Intercalates and exfoliates formed with long chain (C10 +) monomeric organic intercalant compounds; and composite materials containing same

ABSTRACT

Intercalates formed by contacting a layered material, e.g., a phyllosilicate, with an intercalant monomer including an alkyl radical having at least 10 carbon atoms and having a dipole moment greater than the dipole moment of water, to sorb or intercalate the intercalant monomer between adjacent platelets of the layered material. Sufficient intercalant monomer is sorbed between adjacent platelets to expand the adjacent platelets to a spacing of at least about 5 Å (as measured after water removal to a maximum of 5% by weight water), up to about 100 Å and preferably in the range of about 10-45 Å, so that the intercalate easily can be exfoliated into individual platelets. The intercalated complex can be combined with an organic liquid into a viscous carrier material, for delivery of the carrier material, or for delivery of an active compound; or the intercalated complex can be combined with a matrix polymer to form a strong, filled polymer matrix.

FIELD OF THE INVENTION

The present invention is directed to intercalated layered materials, andexfoliates thereof, manufactured by sorption (adsorption and/orabsorption) of one or more long chain (C₁₀ +) monomeric organicintercalant compounds between planar layers of a swellable layeredmaterial, such as a phyllosilicate or other layered material, to expandthe interlayer spacing of adjacent layers to at least about 5 Angstroms(Å), preferably at least about 10 Å. More particularly, the presentinvention is directed to intercalates formed with monomeric intercalantmolecules that are long chain (C₁₀ + alkyl) monomeric organic compoundsthat have a dipole moment at one end of the molecule that is greaterthan the dipole moment of water (greater than 1.85 debyes). Theintercalant molecules are sorbed on the internal surfaces betweenadjacent layers of the planar platelets of a layered material, such as aphyllosilicate, preferably a smectite clay, and, surprisingly, the endof the monomeric molecules having a dipole moment greater than thedipole moment of water coordinate surrounding Na⁺ ions on the innersurface of the phyllosilicate platelets through an electrostaticattraction, e.g., Van Der Waals forces, to form rigid columns of themonomeric molecules that stand perpendicular to the platelet surfaces toprovide surprisingly large basal spacings between adjacentphyllosilicate platelets with relatively few monomeric molecules. Theadjacent, relatively widely spaced platelets of such intercalates, andthe exfoliates thereof, therefore, have a very porous gallery of longchain (C₁₀ + alkyl) molecules extending perpendicularly from theplatelets, resulting in increased sorption (absorption and/oradsorption) of both hydrophilic and hydrophobic molecules by theresulting intercalates and exfoliates thereof; excellent intercalatesand exfoliates for combining with melt polymers (matrix thermoplasticand/or thermosetting polymers) for increased mechanical strength;increased oxygen impermeability in films and sheets; increasedtemperature resistance characteristics; and the like. The long chain(C₁₀ + alkyl), molecules expand the interlayer spacing of thephyllosilicate to at least about 5 Å, preferably at least about 10 Å,more preferably to at least about 20 Å, and most preferably to at leastabout 30-45 Å, up to about 100 Å, or disappearance of periodicity.

The intercalated long chain monomers surprisingly form a unique type ofintercalate and exfoliate that includes rigid extending columns of longchain (C₁₀ + alkyl) monomer molecules that have long chain molecule endsextending perpendicularly from one platelet surface abutting long chainmolecule ends extending perpendicularly from an adjacent plateletsurface to hold the adjacent platelets more widely spaced, with fewerintercalant molecules than any intercalate heretofore known. Theresulting intercalates are neither entirely organophilic nor entirelyhydrophilic, but a combination of the two; have surprising sorption ofhydrophilic and hydrophobic molecules; and easily can be exfoliated andcombined as individual platelets with a polymer to form a compositematerial; or combined with a polar organic solvent carrier to form aviscous composition having a myriad of uses. The resulting intercalateor exfoliate; or polymer/intercalate or polymer/exfoliated plateletcomposite materials are useful as plasticizers; for providing increasedviscosity and elasticity to thermoplastic and thermosetting polymers,e.g., for plasticizing polyvinyl chloride; for food wrap having improvedgas impermeability; for electrical components; for food grade drinkcontainers; for raising the viscosity of polar organic liquids; and foraltering one or more physical properties of a matrix polymer, such aselasticity and temperature characteristics, e.g., glass transitiontemperature and high temperature resistance.

BACKGROUND OF THE INVENTION AND PRIOR ART

It is well known that phyllosilicates, such as smectite clays, e.g.,sodium montmorillonite and calcium montmorillonite, can be treated withorganic molecules, such as organic ammonium ions, to intercalate theorganic molecules between adjacent, planar silicate layers, for bondingthe organic molecules with a polymer, for intercalation of the polymerbetween the layers, thereby substantially increasing the interlayer(interlaminar) spacing between the adjacent silicate layers. Thethus-treated, intercalated phyllosilicates, having interlayer spacingsof at least about 10-20 Å and up to about 100 Angstroms, then can beexfoliated, e.g., the silicate layers are separated, e.g., mechanically,by high shear mixing. The individual silicate layers, when admixed witha matrix polymer, before, after or during the polymerization of thematrix polymer, e.g., a polyamide--see U.S. Pat. Nos. 4,739,007;4,810,734; and 5,385,776--have been found to substantially improve oneor more properties of the polymer, such as mechanical strength and/orhigh temperature characteristics.

Exemplary prior art composites, also called "nanocomposites", aredisclosed in published PCT disclosure of Allied Signal, Inc. WO 93/04118and U.S. Pat. No. 5,385,776, disclosing the admixture of individualplatelet particles derived from intercalated layered silicate materials,with a polymer to form a polymer matrix having one or more properties ofthe matrix polymer improved by the addition of the exfoliatedintercalate. As disclosed in WO 93/04118, the intercalate is formed (theinterlayer spacing between adjacent silicate platelets is increased) byadsorption of a silane coupling agent or an onium cation, such as aquaternary ammonium compound, having a reactive group which iscompatible with the matrix polymer. Such quaternary ammonium cations arewell known to convert a highly hydrophilic clay, such as sodium orcalcium montmorillonite, into an organophilic clay capable of sorbingorganic molecules. A publication that discloses direct intercalation(without solvent) of polystyrene and poly(ethylene oxide) in organicallymodified silicates is Synthesis and Properties of Two-DimensionalNanostructures by Direct Intercalation of Polymer Melts in LayeredSilicates, Richard A. Vaia, et al., Chem. Mater., 5:1694-1696(1993).Also as disclosed in Adv. Materials, 7, No. 2: (1985), pp, 154-156, NewPolymer Electrolyte Nanocomposites: Melt Intercalation of Poly(EthyleneOxide) in Mica-Type Silicates, Richard A. Vaia, et al., poly(ethyleneoxide) can be intercalated directly into Na-montmorillonite andLi-montmorillonite by heating to 80° C. for 2-6 hours to achieve ad-spacing of 17.7 Å. The intercalation is accompanied by displacingwater molecules, disposed between the clay platelets, with polymermolecules. Apparently, however, the intercalated material could not beexfoliated and was tested in pellet form. It was quite surprising to oneof the authors of these articles that exfoliated material could bemanufactured in accordance with the present invention.

Previous attempts have been made to intercalate polyvinylpyrrolidone(PVP), polyvinyl alcohol (PVA) and poly(ethylene oxide) (PEO) betweenmontmorillonite clay platelets with little success. As described inLevy, et al., Interlayer Adsorption of Polyvinylpyrrolidone onMontinorillonite, Journal of Colloid and Interface Science, Vol. 50, No.3, March 1975, pages 442-450, attempts were made to sorb PVP (40,000average M.W.) between monojonic montmorillonite clay platelets (Na, K,Ca and Mg) by successive washes with absolute ethanol, and thenattempting to sorb the PVP by contact with 1% PVP/ethanol/watersolutions, with varying amounts of water, via replacing the ethanolsolvent molecules that were sorbed in washing (to expand the plateletsto about 17.7 Å). Only the sodium montmorillonite had expanded beyond a20 Å basal spacing (e.g., 26 Å and 32 Å), at 5⁺ % H₂ O, after contactwith the PVP/ethanol/H₂ O solution. It was concluded that the ethanolwas needed to initially increase the basal spacing for later sorption ofPVP, and that water did not directly affect the sorption of PVP betweenthe clay platelets (Table II, page 445), except for sodiummontmorillonite. The sorption was time consuming and difficult and metwith little success.

Further, as described in Greenland, Adsorption of Polyvinyl Alcohols byMontmorillonite, Journal of Colloid Sciences, Vol. 18, pages 647-664(1963), polyvinyl alcohols containing 12% residual acetyl groups couldincrease the basal spacing by only about 10 Å due to the sorbedpolyvinyl alcohol (PVA). As the concentration of polymer in theintercalant polymer-containing solution was increased from 0.25% to 4%,the amount of polymer sorbed was substantially reduced, indicating thatsorption might only be effective at polymer concentrations in theintercalant polymer-containing composition on the order of 1% by weightpolymer, or less. Such a dilute process for intercalation of polymerinto layered materials would be exceptionally costly in drying theintercalated layered materials for separation of intercalate from thepolymer carrier, e.g., water, and, therefore, apparently no further workwas accomplished toward commercialization.

In accordance with one embodiment of the present invention, intercalatesare prepared by contacting a phyllosilicate with a monomeric organiccompound having a long chain alkyl radical (C₁₀ + alkyl) and having anelectrostatic functionality on one end of the molecule that provides adipole moment that is greater than the dipole moment of water. Exemplaryof such electrostatic functionalities include a hydroxyl; apolyhydroxyl; a carbonyl such as carboxylic acids, and salts thereof;polycarboxylic acids and salts thereof; aldehydes; ketones; amines;amides; ethers; esters; lactams; lactones; anhydrides; nitrites; n-alkylhalides; pyridines; and mixtures thereof.

In accordance with an important feature of the present invention, bestresults are achieved by mixing the layered material with a polarmonomeric organic intercalant compound, having a C₁₀ + alkyl group and adipole moment on one end of the molecule greater than the dipole momentof water, or greater than 1.85 debyes (>1.85 D), in a concentration ofat least about 2%, preferably at least about 5% by weight polar, longchain alkyl monomeric organic intercalant compound, more preferably atleast about 10% by weight polar, long chain alkyl monomeric organicintercalant compound, and most preferably about 30% to about 80% byweight, based on the weight of polar, long chain alkyl monomeric organicintercalant compound and carrier (e.g., water, with or without anorganic solvent for the polar, long chain alkyl monomeric compound) toachieve better sorption of the monomeric organic intercalant compoundbetween the platelets of the layered material. Dipole moments can befound, or calculated, in accordance with the publication "SelectedValues of Electric Dipole Moments for Molecules in the Gas Phase",Nelson, Lide and Maryott, National Reference Data Series--NationalBureau of Standards (NSRDS-NBS 10), hereby incorporated by reference.The publication is available from the Superintendent of Documents, U.S.Government Printing Office, Washington, D.C., 20402. One debye unit(D)=10⁻¹⁸ electrostatic units of charge×centimeters. The conversionfactor to the Systeme International is 1D=3.33564 ×10⁻²⁴ coulombmeter.Regardless of the concentration of monomeric organic intercalantcompound in aqueous liquid, the intercalating composition should have apolar, long chain monomeric organic intercalant compound:layeredmaterial weight ratio of at least 1:20, preferably at least 1:10, morepreferably at least 1:5, and most preferably about 1:4 to achieveelectrostatic complexing of the electrostatic monomeric organicintercalant compound with an inner surface of a platelet of the layeredmaterial to achieve efficient intercalation of the monomeric organicintercalant compound between adjacent platelets of the layered material.The polar, long chain (C₁₀ + alkyl) monomeric organic intercalantcompound sorbed between and bonded to (complexed with) the silicateplatelets causes surprising separation or added spacing between adjacentsilicate platelets.

For simplicity of description, the above-described C₁₀ + alkyl monomericorganic intercalant compounds having at least one molecule end that hasa dipole moment greater than the dipole moment of water are hereinaftercalled the "intercalant" or "intercalant monomer" or "monomerintercalant". The monomer intercalant will be sorbed sufficiently toincrease the interlayer spacing of the phyllosilicate in the range ofabout 5 Å to about 100 Å, preferably at least about 10 Å for easier andmore complete exfoliation, in a commercially viable process, regardlessof the particular layered material, e.g., phyllosilicate, or intercalantmonomer.

In accordance with the present invention, it has been found that aphyllosilicate, such as a smectite clay, can be intercalatedsufficiently for subsequent exfoliation by sorption of organic monomercompounds that have an alkyl group of at least 10 carbon atoms, andinclude one end of the molecule having a dipole moment greater than thedipole moment of water to provide bonding between a polar end of one ortwo intercalant monomer molecules and the Na⁺ cations of the innersurfaces of the platelets of the layered material, e.g., phyllosilicate.Sorption and metal cation attraction or bonding between two polar endgroups of the intercalant monomer molecules and the interlayer Na⁺cations of the phyllosilicate; or the bonding between the interlayer Na⁺cations in hexagonal or pseudohexagonal rings of the smectite plateletlayers and an intercalant monomer aromatic ring structure, is providedby a mechanism selected from the group consisting of ionic complexing;electrostatic complexing; chelation; hydrogen bonding; ion-dipole;dipole/dipole; Van Der Waals forces; and any combination thereof.

Such bonding, via one or more metal (Na⁺) cations of the phyllosilicatesharing electrons with one or two electronegative atoms of one or twopolar ends of C₁₀ + alkyl monomer intercalant molecules, on an innersurface of one or both adjacent phyllosilicate platelets surprisinglyprovides rigid intercalant monomer molecules extending perpendicularlyfrom the phyllosilicate platelet surfaces, and increases the interlayerspacing between adjacent silicate platelets or other layered material toat least about 5 Å, preferably to at least about 10 Å, more preferablyto at least about 20 Å, and most preferably in the range of about 30 Åto about 45 Å, while consuming surprisingly little monomer intercalantin relation to the increased basal spacing achieved. The electronegativeatoms at the polar end of the intercalant monomer molecules thatcoordinate to surround the platelet Na⁺ ions can be, for example,oxygen, sulfur, nitrogen, halogen, and combinations thereof.

Such intercalated phyllosilicates easily can be exfoliated intoindividual phyllosilicate platelets before or during admixture with aliquid carrier or solvent, for example, one or more monohydric alcohols,such as methanol, ethanol, propanol, and/or butanol; polyhydricalcohols, such as glycerols and glycols, e.g., ethylene glycol,propylene glycol, butylene glycol, glycerine and mixtures thereof;aldehydes; ketones; carboxylic acids; amines; amides; and other organicsolvents, for delivery of the solvent in a thixotropic composition, orfor delivery of any active hydrophobic or hydrophilic organic compound,such as a topically active pharmaceutical, dissolved or dispersed in thecarrier or solvent, in a thixotropic composition; or the intercalatesand/or exfoliates thereof can be admixed with a polymer or other organicmonomer compound(s) or composition to increase the viscosity of theorganic compound or provide a polymer/intercalate and/orpolymer/exfoliate composition to enhance one or more properties of amatrix polymer.

DEFINITIONS

Whenever used in this Specification, the terms set forth shall have thefollowing meanings:

"Layered Material" shall mean an inorganic material, such as a smectiteclay mineral, that is in the form of a plurality of adjacent, boundlayers and has a thickness, for each layer, of about 3 Å to about 50 Å,preferably about 10 Å.

"Platelets" shall mean individual layers of the Layered Material.

"Intercalate" or "Intercalated" shall mean a Layered Material thatincludes long chain alkyl (C₁₀ + alkyl) organic monomer moleculesdisposed between adjacent platelets of the Layered Material to increasethe interlayer spacing between the adjacent platelets to at least about5 Å, preferably at least about 10 Å.

"Intercalation" shall mean a process for forming an Intercalate.

"Intercalant Monomer" or "Intercalant" or "Monomer Intercalant" shallmean a monomeric organic compound that includes a long chain alkyl(C₁₀ + alkyl) group and includes, at one end of the molecule, a polarmoiety that provides the molecule with a dipole moment that is greaterthan the dipole moment of water. Suitable polar moieties include, forexample, a moiety selected from the group consisting of a hydroxyl; apolyhydroxyl; a carbonyl; a carboxylic acid; an amine; an amide; anether; an ester; lactams; lactones; anhydrides; nitrites; n-alkylhalides; pyridines; and mixtures thereof that is sorbed betweenPlatelets of the Layered Material and complexes with the Na⁺ cations onthe platelet surfaces to form an Intercalate.

"Intercalating Carrier" shall mean a carrier comprising water with orwithout an organic solvent used together with an Intercalant Monomer toform an Intercalating Composition capable of achieving Intercalation ofthe Layered Material.

"Intercalating Composition" or "Intercalant Composition" shall mean acomposition comprising an Intercalant Monomer, an Intercalating Carrierfor the Intercalant Monomer, and a Layered Material.

"Exfoliate" or "Exfoliated" shall mean individual platelets of anIntercalated Layered Material so that adjacent platelets of theIntercalated Layered Material can be dispersed individually throughout acarrier material, such as water, a polymer, an alcohol or glycol, or anyother organic solvent.

"Exfoliation" shall mean a process for forming an Exfoliate from anIntercalate.

"Nanocomposite" shall mean a mixture that includes a monomer, polymer,oligomer, or copolymer having dispersed therein a plurality ofindividual platelets obtained from an exfoliated Intercalated LayeredMaterial.

"Matrix Monomer" shall mean a monomer that the Intercalate or Exfoliateis mixed with or dispersed.

"Matrix Polymer" shall mean a thermoplastic or thermosetting polymer inwhich the Intercalate and/or Exfoliate is mixed or dispersed to form aNanocomposite.

SUMMARY OF THE INVENTION

In brief, the present invention is directed to intercalates andexfoliates thereof formed by contacting a layered phyllosilicate with along chain alkyl (C₁₀ + alkyl) organic monomer (intercalant monomer),having an alkyl group of at least 10 carbon atoms, and having a dipolemoment at one end of the molecule that is greater than the dipole momentof water. Suitable long chain intercalant monomers include a polar endhaving at least one hydroxyl functionality; a carbonyl functionality; acarboxylic acid functionality; an amine functionality; an amidefunctionality; an ether functionality; an ester functionality; lactams;lactones; anhydrides; nitrites; n-alkyl halides; and/or pyridines; tosorb or intercalate the intercalant monomer or mixtures of intercalantmonomers between adjacent platelets of a layered inorganic material,e.g., a phyllosilicate.

Sufficient intercalant monomer is sorbed between adjacent phyllosilicateplatelets to expand the spacing between adjacent platelets (interlayerspacing) to a distance of at least about 5 Å, preferably to at leastabout 10 Å (as measured after water removal to a maximum water contentof 5% by weight, based on the dry weight of the layered material) andmore preferably in the range of about 30-45 Å, so that the intercalateeasily can be exfoliated, sometimes naturally without shearing beingnecessary. At times, the intercalate requires shearing that easily canbe accomplished, e.g., when mixing the intercalate with a polar organicsolvent carrier, such as a polar organic hydrocarbon, and/or with apolymer melt to provide a platelet-containing composite material ornanocomposite--the platelets being obtained by exfoliation of theintercalated layered-material, e.g., phyllosilicate.

The intercalant monomer has an affinity for the Na⁺ cations on the innersurfaces of the phyllosilicate platelets so that it is sorbed between,and is maintained associated with the silicate platelets in theinterlayer spaces, and is complexed to the platelet surfaces afterexfoliation. In accordance with the present invention, the intercalantmonomer should include a molecule end that has a dipole moment greaterthan the dipole moment of water to be sufficiently bound to thephyllosilicate platelet surface, it is hereby theorized, by a mechanismselected from the group consisting of ionic complexing; electrostaticcomplexing; chelation; hydrogen bonding; ion-dipole; dipole/dipole; VanDer Waals forces; and any combination thereof. Such bonding, via a metalcation, e.g., Na⁺, of the phyllosilicate inner platelet surface sharingelectrons with electronegative atoms of a polar end of the long chain,monomeric organic intercalant compound, provides adherence between theintercalant monomer molecules and the platelet inner surfaces of thelayered material. The electronegative atoms on the polar end of theintercalant monomer can be, for example, oxygen, sulfur, nitrogen,halogen, and combinations thereof. Atoms having a sufficientelectronegativity to bond to metal cations on the inner surface of theplatelets have an electronegativity of at least 2.0, and preferably atleast 2.5, on the Pauling Scale. A "polar moiety" or "polar group" isdefined as a moiety having two adjacent atoms that are bonded covalentlyand have a difference in electronegativity of at least 0.5electronegativity units on the Pauling Scale.

Such intercalant monomers have sufficient affinity for thephyllosilicate platelets to maintain sufficient interlayer spacing forexfoliation, without the need for coupling agents or spacing agents,such as the onium ion or silane coupling agents disclosed in theabove-mentioned prior art. Consequently, in accordance with the presentinvention, the phyllosilicate inner platelet surfaces need not be firstreacted with an onium ion or silane coupling agent in order to complexthe intercalant monomer to the inner platelet surfaces. A schematicrepresentation of the charge distribution on the surfaces of a sodiummontmorillonite clay is shown in FIGS. 1-3. As shown in FIGS. 2 and 3,the location of surface Na⁺ cations with respect to the location ofoxygen (Ox), Mg, Si and Al atoms (FIGS. 1 and 2) results in a claysurface charge distribution as schematically shown in FIG. 3. Thepositive-negative charge distribution over the entire clay surfaceprovides for excellent dipole/dipole attraction of the above-describedlong chain, polar organic monomer intercalants on the surfaces of theclay platelets.

The intercalate-containing and/or exfoliate-containing compositions canbe in the form of a stable thixotropic gel that is not subject to phaseseparation and can be used to deliver any active materials, such as inthe cosmetic, hair care and pharmaceutical industries. The layeredmaterial is intercalated and optionally exfoliated by contact with anintercalant monomer and water, such as by mixing and/or extruding theintercalant composition to intercalate the monomer between adjacentphyllosilicate platelets and optionally separate (exfoliate) the layeredmaterial into individual platelets. The amount of water varies,depending upon the amount of shear imparted to the layered material incontact with the intercalant monomer and water. In one method, theintercalating composition is pug milled or extruded at a water contentof about 25% by weight to about 50% by weight water, preferably about35% to about 40% by weight water, based on the dry weight of the layeredmaterial, e.g., clay. In another method, the clay and water areslurried, with at least about 25% by weight water, preferably at leastabout 65% by weight water, based on the dry weight of the layeredmaterial, e.g., preferably less than about 20% by weight clay in water,based on the total weight of layered material and water, more preferablyless than about 10% layered material in water, with the addition ofabout 2% by weight to about 90% by weight intercalant monomer, based onthe dry weight of the layered material.

Sorption of the intercalant monomer should be sufficient to achieveexpansion of adjacent platelets of the layered material (when measureddry) to an interlayer spacing of at least about 5 Å, preferably to aspacing of at least about 10 Å, more preferably a spacing of at leastabout 20 Å, and most preferably a spacing of about 30-45 Å. To achieveintercalates that can be exfoliated easily using the monomerintercalants disclosed herein, the weight ratio of intercalant monomerto layered material, preferably a water-swellable smectite clay such assodium bentonite, in the intercalating composition should be at leastabout 1:20, preferably at least about 1:12 to 1:10, more preferably atleast about 1:5, and most preferably about 1:5 to about 1:3. It ispreferred that the concentration of intercalant monomer in theintercalating composition, based on the total weight of intercalantmonomer plus intercalant carrier (water plus any organic liquid solvent)in the intercalating composition is at least about 15% by weight, morepreferably at least about 20% by weight intercalant monomer, for exampleabout 20-30% to about 90% by weight intercalant monomer, based on theweight of intercalant monomer plus intercalating carrier in theintercalating composition during intercalation of the layered material.

Surprising results are achieved when the molar ratio of intercalantmonomer to phyllosilicate (sodium) are at least 2:1, particularly at 3:1or greater. Basal spacings that result from such molar ratios are fargreater than have ever been achieved using the same ratios of otherintercalant monomers.

Interlayer spacings sufficient for exfoliation are achieved by directintercalation of the above-defined intercalant monomers, without priorsorption of an onium or silane coupling agent, and provide easier andmore complete exfoliation for or during incorporation of the plateletsinto a polar organic compound or a polar organic compound-containingcomposition carrier or solvent to provide unexpectedly viscous carriercompositions, for delivery of the carrier or solvent, or foradministration of an active compound that is dissolved or dispersed inthe carrier or solvent. Such compositions, especially the high viscositygels, are particularly useful for delivery of active compounds, such asoxidizing agents for hair waving lotions, and drugs for topicaladministration, since extremely high viscosities are obtainable; and foradmixtures of the platelets with polar solvents in modifying rheology,e.g., of cosmetics, oil-well drilling fluids, paints, lubricants,especially food grade lubricants, in the manufacture of oil and grease,and the like. Such intercalates and/or exfoliates also are especiallyuseful in admixture with matrix thermoplastic or thermosetting polymersin the manufacture of polymeric articles from the polar organiccarrier/polymer/intercalate and/or platelet composite materials.

Once exfoliated, the platelets of the intercalate are predominantlycompletely separated into individual platelets and the originallyadjacent platelets no longer are retained in a parallel, spaceddisposition, but are free to move as predominantly individualintercalant monomer-coated (continuously or discontinuously) plateletsthroughout a polymer melt for enhancing one or more properties, such asstrength or temperature resistance; or for mixing with a carrier orsolvent material to maintain viscosity and thixotropy of the carriermaterial. The predominantly individual phyllosilicate platelets, havingtheir platelet surfaces complexed with intercalant monomer molecules,are randomly, homogeneously and uniformly dispersed, predominantly asindividual platelets, throughout the carrier or solvent to achieve newand unexpected viscosities in the carrier/platelet compositions evenafter addition of an active organic compound, such as a cosmeticcomponent or a medicament, for administration of the active organiccompound(s) from the composition.

As recognized, the thickness of the exfoliated, individual platelets(about 10 Å) is relatively small compared to the size of the flatopposite platelet faces. The platelets have an aspect ratio in the rangeof about 200 to about 2,000. Dispersing such finely divided plateletparticles into a polymer melt or into a polar organic liquid carrierimparts a very large area of contact between polymer melt or carrier andplatelet particles, for a given volume of particles in the composite,and a high degree of platelet homogeneity in the composite material.Platelet particles of high strength and modulus, dispersed at sub-micronsize (nanoscale), impart greater mechanical reinforcement to a polymerand a higher viscosity to a polar organic liquid carrier than docomparable loadings of conventional reinforcing fillers of micron size,and can impart lower permeability to matrix polymers than do comparableloadings of conventional fillers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a top view of sodiummontmorillonite clay showing the ionic charge distribution for thesodium montmorillonite clay top and interlayer surfaces showing Na⁺ ionsas the largest circles as well as magnesium and aluminum ions and Si andoxygen (Ox) atoms disposed beneath the sodium ions;

FIG. 2 is a side view (bc-projection) of the schematic representation ofFIG. 1;

FIG. 3 is a schematic representation of the charge distribution on thesurfaces of sodium montmorillonite clay platelets showing thedistribution of positive and negative charges on the clay plateletsurfaces as a result of the natural disposition of the Na, Mg, Al, Si,and oxygen (Ox) atoms of the clay shown in FIGS. 1 and 2;

FIG. 4 is a schematic representation of a side view of a sodium cation(largest ball) showing three dodecyl pyrrolidone intercalant monomermolecules ionically complexed and coordinated therearound, with the longchain (C₁₂) alkyl groups extending perpendicularly from amontmorillonite platelet surface;

FIG. 5 is an x-ray diffraction pattern for a complex of 10% by weight ofdodecyl pyrrolidone and 90% by weight sodium montmorillonite clay;

FIG. 6 is an x-ray diffraction pattern for a complex of 20% by weight ofdodecyl pyrrolidone and 80% by weight sodium montmorillonite clay;

FIG. 7 is an x-ray diffraction pattern for a complex of 30% by weight ofdodecyl pyrrolidone and 70% by weight sodium montmorillonite clay;

FIG. 8 is an x-ray diffraction pattern for a complex of 40% by weight ofdodecyl pyrrolidone and 60% by weight sodium montmorillonite clay;

FIG. 9 is an x-ray diffraction pattern for a complex of 50% by weight ofdodecyl pyrrolidone and 50% by weight sodium montmorillonite clay;

FIG. 10 is an x-ray diffraction pattern for a complex of 60% by weightof dodecyl pyrrolidone and 40% by weight sodium montmorillonite clay;

FIG. 11 is an x-ray diffraction pattern for a complex of 80% by weightof dodecyl pyrrolidone and 20% by weight sodium montmorillonite clay;

FIG. 12 is an x-ray diffraction pattern for a complex of 30% dodecylaldehyde and 70% sodium montmorillonite clay; and

FIG. 13 is a graph showing flexural modulus versus temperature for thedodecyl pyrrolidone (DDP) complex of Example 2 added to a polybutyleneterephthalate matrix polymer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

To form the intercalated and exfoliated materials of the presentinvention, the layered material, e.g., the phyllosilicate, should beswelled or intercalated by sorption of an intercalant monomer thatincludes an alkyl group having at least 10 carbon atoms, and includes asecond molecule end that has a dipole moment that is greater than thedipole moment of water. In accordance with a preferred embodiment of thepresent invention, the phyllosilicate should include at least 4% byweight water, up to about 5,000% by weight water, based on the dryweight of the phyllosilicate, preferably about 7% to about 100% water,more preferably about 25% to about 50% by weight water, prior to orduring contact with the intercalant monomer to achieve sufficientintercalation for exfoliation. Preferably, the phyllosilicate shouldinclude at least about 4% by weight water before contact with theintercalating carrier for efficient intercalation. The amount ofintercalant monomer in contact with the phyllosilicate from theintercalating composition, for efficient exfoliation, should provide anintercalant monomer/phyllosilicate weight ratio (based on the dry weightof the phyllosilicate) of at least about 1:20, preferably at least about3.2/20, and more preferably about 4-14/20, to provide efficient sorptionand complexing (intercalation) of the intercalant monomer between theplatelets of the layered material, e.g., phyllosilicate.

The monomer intercalants are introduced in the form of a solid or liquidcomposition (neat or aqueous, with or without an organic solvent, e.g.,an aliphatic hydrocarbon, such as heptane) having an intercalant monomerconcentration of at least about 2%, preferably at least about 5% byweight intercalant monomer, more preferably at least about 50% to about100% by weight intercalant monomer in the intercalating composition,based on the dry weight of the layered material, for intercalant monomersorption. The intercalant monomer can be added as a solid with theaddition to the layered material/intercalant monomer blend of about 20%water, preferably at least about 30% water to about 5,000% water ormore, based on the dry weight of layered material. Preferably about 30%to about 50% water, more preferably about 30% to about 40% water, basedon the dry weight of the layered material, is included in theintercalating composition when extruding or pug milling, so that lesswater is sorbed by the intercalate, thereby necessitating less dryingenergy after intercalation. The monomer intercalants may be introducedinto the spaces between every layer, nearly every layer, or at least apredominance of the layers of the layered material such that thesubsequently exfoliated platelet particles are preferably, predominantlyless than about 5 layers in thickness; more preferably, predominantlyabout 1 or 2 layers in thickness; and most preferably, predominantlysingle platelets.

Any swellable layered material that sufficiently sorbs the intercalantmonomer to increase the interlayer spacing between adjacentphyllosilicate platelets to at least about 5 Å, preferably to at leastabout 10 Å (when the phyllosilicate is measured dry) may be used in thepractice of this invention. Useful swellable layered materials includephyllosilicates, such as smectite clay minerals, e.g., montmorillonite,particularly sodium montmorillonite; magnesium montmorillonite and/orcalcium montmorillonite; nontronite; beidellite; volkonskoite;hectorite; saponite; sauconite; sobockite; stevensite; svinfordite;vermiculite; and the like. Other useful layered materials includemicaceous minerals, such as illite and mixed layered illite/smectiteminerals, such as rectorite, tarosovite, ledikite and admixtures ofillites with the clay minerals named above.

Other layered materials having little or no charge on the layers may beuseful in this invention provided they can be intercalated with theintercalant monomers to expand their interlayer spacing to at leastabout 5 Å, preferably to at least about 10 Å. Preferred swellablelayered materials are phyllosilicates of the 2:1 type having a negativecharge on the layers ranging from about 0.15 to about 0.9 charges performula unit and a commensurate number of exchangeable metal cations inthe interlayer spaces. Most preferred layered materials are smectiteclay minerals such as montmorillonite, nontronite, beidellite,volkonskoite, hectorite, saponite, sauconite, sobockite, stevensite, andsvinfordite.

As used herein the "interlayer spacing" refers to the distance betweenthe internal faces of the adjacent layers as they are assembled in thelayered material before any delamination (exfoliation) takes place. Theinterlayer spacing is measured when the layered material is "air dry",e.g., contains about 3-6% by weight water, e.g., 5% by weight waterbased on the dry weight of the layered material. The preferred claymaterials generally include interlayer cations such as Na⁺, Ca⁺², K⁺,Mg⁺², NH₄ ⁺ and the like, including mixtures thereof.

The amount of intercalant monomer intercalated into the swellablelayered materials useful in this invention, in order that theintercalated layered material platelets surfaces sufficiently complexwith the intercalant monomer molecules such that the layered materialmay be easily exfoliated or delaminated into individual platelets, mayvary substantially between about 2%, preferably at least about 10%, andabout 90%, based on the dry weight of the layered silicate material. Inthe preferred embodiments of the invention, amounts of monomerintercalants employed, with respect to the dry weight of layeredmaterial being intercalated, will preferably range from about 8 grams ofintercalant monomer:100 grams of layered material (dry basis),preferably at least about 10 grams of intercalant monomer:100 grams oflayered material to about 80-90 grams intercalant monomer:100 grams oflayered material. More preferred amounts are from about 20 gramsintercalant monomer:100 grams of layered material to about 60 gramsintercalant monomer:100 grams of layered material (dry basis).

The monomer intercalants are introduced into (sorbed within) theinterlayer spaces of the layered material in one of two ways. In apreferred method of intercalating, the layered material is intimatelymixed, e.g., by extrusion or pug milling, to form an intercalatingcomposition comprising the layered material, in an intercalantmonomer/water solution, or intercalant monomer, water and an organiccarrier for the intercalant monomer. To achieve sufficient intercalationfor exfoliation, the layered material/intercalant monomer blend containsat least about 8% by weight, preferably at least about 10% by weightintercalant monomer, based on the dry weight of the layered material.The intercalant monomer carrier (preferably water, with or without anorganic solvent) can be added by first solubilizing or dispersing theintercalant monomer in the carrier; or a dry intercalant monomer andrelatively dry phyllosilicate (preferably containing at least about 4%by weight water) can be blended and the intercalating carrier added tothe blend, or to the phyllosilicate prior to adding the dry intercalantmonomer. In every case, it has been found that surprising sorption andcomplexing of intercalant monomer between platelets is achieved atrelatively low loadings of intercalating carrier, especially H₂ O, e.g.,at least about 4% by weight water, based on the dry weight of thephyllosilicate. When intercalating the phyllosilicate in slurry form(e.g., 900 pounds water, 100 pounds phyllosilicate, 25 poundsintercalant monomer) the amount of water can vary from a preferredminimum of at least about 30% by weight water, with no upper limit tothe amount of water in the intercalating composition (the phyllosilicateintercalate is easily separated from the intercalating composition).

Alternatively, the intercalating carrier, e.g., water, with or withoutan organic solvent, can be added directly to the phyllosilicate prior toadding the intercalant monomer, either dry or in solution. Sorption ofthe monomer intercalant molecules may be performed by exposing thelayered material to dry or liquid intercalant monomers in theintercalating composition containing at least about 2% by weight,preferably at least about 5% by weight intercalant monomer, morepreferably at least about 50% intercalant monomer, based on the dryweight of the layered material. Sorption may be aided by exposure of theintercalating composition to heat, pressure, ultrasonic cavitation, ormicrowaves.

In accordance with another method of intercalating the intercalantmonomer between the platelets of the layered material and exfoliatingthe intercalate, the layered material, containing at least about 4% byweight water, preferably about 10% to about 15% by weight water, isblended with a water and/or organic solvent solution of an intercalantmonomer in a ratio sufficient to provide at least about 8% by weight,preferably at least about 10% by weight intercalant monomer, based onthe dry weight of the layered material. The blend then preferably isextruded for faster intercalation of the intercalant monomer with thelayered material.

The intercalant monomer has an affinity for the phyllosilicate, as shownin FIG. 4, so that it is sorbed between, and is maintained associatedwith the cations on the inner surfaces of the silicate platelets, in theinterlayer spaces, and remains complexed to the platelet surface afterexfoliation. In accordance with the present invention, the intercalantmonomer should include a polar end having a dipole moment greater thanthe dipole moment of water to be sufficiently bound to the plateletsurfaces, it is hereby theorized, by a mechanism selected from the groupconsisting of ionic complexing; electrostatic complexing; chelation;hydrogen bonding; ion-dipole; dipole/dipole; Van Der Waals forces; andany combination thereof. Such bonding, via a metal cation (e.g., Na⁺) ofthe phyllosilicate sharing electrons with electronegative atoms of oneor monomer polar intercalant molecule ends of one or two intercalantmonomer molecules, to an inner surface of the phyllosilicate plateletsprovides adherence between the polar intercalant monomer molecule endsand the platelet inner surfaces of the layered material. Suchintercalant monomers have sufficient affinity for the phyllosilicateplatelets to maintain sufficient interlayer spacing for exfoliation,without the need for coupling agents or spacing agents, such as theonium ion or silane coupling agents disclosed in the above-mentionedprior art.

As shown in FIGS. 1-3, the disposition of surface Na⁺ ions with respectto the disposition of oxygen (Ox), Mg, Si, and Al atoms, and the naturalclay substitution of Mg⁺² cations for Al⁺³ cations, leaving a netnegative charge at the sites of substitution, results in a clay surfacecharge distribution as shown in FIG. 3. This alternating positive tonegative surface charge over spans of the clay platelets surfaces, andon the clay platelet surfaces in the interlayer spacing, provide forexcellent dipole/dipole attraction of a polar intercalant monomermolecule, as shown schematically in FIG. 4, for intercalation of theclay and for bonding or complexing of such polar molecules on theplatelet surfaces, after exfoliation.

It is preferred that the platelet loading be less than about 10% forpurposes of increasing the viscosity of an organic liquid carrier.Platelet particle loadings within the range of about 0.05% to about 40%by weight, preferably about 0.5% to about 20%, more preferably about 1%to about 10% of the composite material significantly enhances viscosity.In general, the amount of platelet particles incorporated into a liquidcarrier, such as a polar solvent, e.g., a glycol such as glycerol, isless than about 90% by weight of the mixture, and preferably from about0.01% to about 80% by weight of the composite material mixture, morepreferably from about 0.05% to about 40% by weight of the mixture, andmost preferably from about 0.05% to about 20% or 0.05% to about 10% byweight.

In accordance with an important feature of the present invention, theintercalated phyllosilicate can be manufactured in a concentrated form,e.g., 10-90%, preferably 20-80% intercalant monomer with or withoutanother polar organic compound carrier and 10-90%, preferably 20-80%intercalated phyllosilicate that can be dispersed in the polar organiccarrier and exfoliated before or after addition to the carrier to adesired platelet loading.

Polar organic compounds containing one or more hydroxy functionalitiesare suitable for use as intercalant monomers so long as the hydroxy endof the molecule has a dipole moment greater than the dipole moment ofwater (>1.85 D), and the polar organic compounds have a long chain (C₁₀+) alkyl radical. Examples include long chain (C₁₀ +) alcohols having adipole moment greater than 1.85 D, including aliphatic alcohols;aromatic alcohols; aryl substituted aliphatic alcohols; alkylsubstituted aromatic alcohols; and polyhydric alcohols, such as thephenols, containing a long chain (C₁₀ +) alkyl group.

Detergent range aliphatic alcohols having an alkyl radical of at least10 carbon atoms include the C₁₀ -C₂₄ alcohols, such as the C₁₀ -C₁₈alcohols manufactured from coconut, tallow and/or palm oils; C₁₆, C₁₈oleyl alcohols; C₁₀ -C₁₅ mixed alcohols, C₁₀ -C₂₂ mixed alcohols; andC₁₃, C₁₅ alcohols manufactured from ethylene and other olefins.Additional detergent range alcohols include lauryl alcohol; myristylalcohol; cetyl alcohol; tallow alcohol; stearyl alcohol; and oleylalcohol. Branched detergent range alcohols, such as tridecyl alcohol(C₁₃ H₂₈ O), consisting predominantly of tetramethyl-1-nonanols also aresuitable as the intercalant monomer and/or as a polar organic liquidcarrier. Plasticizer range alcohols include decanol (C₁₀ H₂₂ O); andtridecyl alcohol (C₁₃ H₂₈ O).

The nanocomposites containing one or more detergent range alcohols asthe matrix monomer (the phyllosilicate platelets are dispersed in one ormore detergent range alcohols as the polar organic liquid carrier) areuseful, for example, the following industries shown in Table 1.

                  TABLE 1    ______________________________________    INDUSTRY           USE    ______________________________________    detergent          emollient, foam control,                       opacifier, softener    petroleum and lubrication                       drilling mud    agriculture        evaporation suppressant    plastics           mold-release agent,                       antifoam, emulsion                       polymerization agent,                       lubricant    textile            lubricant, foam control,                       anti-static agent, ink                       ingredient; fabric                       softeners    cosmetics          softener, emollient    pulp and paper     foam control    food               water evaporation                       suppressant    rubber             plasticizer, dispersant    paint and coatings foam control    metal working      lubricant, rolling oil    mineral processing flotation agent    ______________________________________

The plasticizer range alcohols (C₁₀ +) are primarily used inplasticizers, e.g., for polyvinyl chloride (PVC) and other resins, butthey also have a wide range of uses in other industrial and consumerproducts, as shown in Table 2.

                  TABLE 2    ______________________________________    INDUSTRY           USE    ______________________________________    plastics           emulsion polymerization    petroleum and lubrication                       defoamer    agriculture        stabilizer, tobacco                       sucker control,                       herbicide, fungicide    mineral processing solvent, extractant,                       antifoam    textile            leveling agent, defoamer    coatings           solvent, smoothing agent    metal working      solvent, lubricant,                       protective coating    chemical processing                       antifoam, solvent    food               moisturizer    cosmetics          perfume ingredient    ______________________________________

Representative Straight-Chain Alkanoic Acids, C_(n) H_(2n) O₂ SystematicName (Common Name)

Decanoic ( capric!); undecanoic ( undecylic!); dodecanoic (lauric);tridecanoic ( tridecylic!); tetradecanoic (myristic); pentadecanoic (pentadecylic!); hexadecanoic (palmitic); heptadecanoic (margaric);octadecanoic (stearic); nonadecanoic ( nonadecyclic!); eicosanoic(arachidic); docosanoic (behenic); tetracosanoic (lignoceric);hexacosanoic (cerotic); octacosanoic (montanic); triacontanoic(melissic); tritriacontanoic (psyllic); and pentatriacontanoic(ceroplastic).

Representative Straight-Chain Alkenoic Acids, C_(n) H.sub.(2n-2) O₂Systematic Name (Common Name)

Trans-4-decenoic; cis-4-decenoic; 9-decenoic (caproleic); 10-undecenoic(undecylenic); trans-3-dodecenoic (linderic); tridecenoic;cis-9-tetradecenoic (myristoleic); pentadecenoic; cis-9-hexadecenoic(cis-9-palmitoleic); trans-9-hexadecenoic (trans-9-palmitoleic);9-heptadecenoic; cis-6-octadecenoic (petroselinic); trans-6-octadecenoic(petroselaidic); cis-9-octadecenoic (oleic); trans-9-octadecenoic(elaidic); cis-11-octadecenoic; trans-11-octadecenoic (vaccenic);cis-5-eicosenoic; cis-9-eicosenoic (gadoleic); cis-11-docosenoic(cetoleic); cis-13 docosenoic (erucic); trans-13-docosenoic (brassidic);cis-15-tetracosenoic (selacholeic); cis-17-hexacosenoic (ximenic); andcis-21-triacontenoic (lumequeic).

Representative Polyunsaturated Fatty Acids Systematic Name (Common Name)Representative Dienoic Acids, C_(n) H_(2n-4) O₂

Trans- 2,4-decadienoic, trans-2,4-dodecadienoic;cis-9,cis-12-octadecadienoic (linoleic);trans-9,trans-12-octadecadienoic (linolelaidic); 5,6-octadecadienoic(laballenic); and 5,13-docosadienoic.

Representative Trienoic Acids, C_(n) H_(2n-6) O₂

6,10,14-hexadecatrienoic (hiragonic);cis-9,cis-12,cis-15-octadecatrienoic (linolenic); cis-9,trans-11,trans-13-octadecatrienoic (α-eleostearic);trans-9,trans-11,trans-13-octadecatrienoic (β-eleostearic);cis-9,cis-11,trans-13-octadecatrienoic (punicic); and trans-9,trans-12,trans-15-octadecatrienoic (linolenelaidic).

Representative Tetraenoic Acids, C_(n) H_(2N-8) O₂

4,8,12,15 octadecatetraenoic (moroctic); cis-9,trans-11,trans-13,cis-15-octadecatetraenoic (α-parinaric); trans-9,trans-11,trans-13,trans-15-octadecatetraenoic (β-parinaric); and5,8,11,14-eicosatetraenoic (arachidonic).

Representative Substituted Acids Systematic Name (Common Name)

2,15,16-trihydroxyhexadecanoic (ustilic); 9,10,16-trihydroxyhexadecanoic(aleuritic); 16-hydroxy-7-hexadecenoic (ambrettolic);12-hydroxy-cis-9-octadecenoic (ricinoleic);12-hydroxy-trans-9-octadecenoic (ricinelaidic);4-oxo-9,11,13-octadecatrienoic (licanic); 9,10-dihydroxyoctadecanoic;12-hydroxyoctadecanoic; 12-oxooctadecanoic;18-hydroxy-9,11,13-octadecatrienoic (kamlolenic);12,13-epoxy-cis-9-octadecenoic (vernolic);8-hydroxy-trans-11-octadecene-9-ynoic (ximenynolic);8-hydroxy-17-octadecene-9,11-diynoic (isanolic); and14-hydroxycis-11-eicosenoic (lesquerolic).

Representative Long Chain (C₁₀ +) Carboxylic Acids And Uses

    ______________________________________    ACID              USES    ______________________________________    canola            surfactants    castor oil acids  lubricating greases    (ricinoleic,    12-hydroxystearic)    coconut oil acids surfactants, soap    hydrogenated and/or                      metallic stearates    separated tallow-based                      (plastic lubricants),    acids             tires, candles, crayons,                      cosmetics    soybean oil acids alkyd resins (paint)    tall oil acids    alkyd resins, ore    2% or more rosin  flotation    less than 2% tallow                      soap, lubricants, fabric    fatty acids       softeners, asphalt                      emulsifiers, synthetic                      rubber, plastics    capric            synthetic lubricants,                      medium-chain triglycerides    caprylic          synthetic lubricants,                      medium-chain triglycerides    caprylic-capric blend                      synthetic lubricants,                      medium-chain triglycerides    lauric, 95%       surfactants, soap    (dodecanoic)    myristic, 95%     esters for cosmetics,    (tetradecanoic)   lotions    oleic             surfactants, lubricants,                      plasticizers    palmitic, 90%     esters for personal care                      products    pelargonic (nonanoic)                      synthetic lubricants,    stearic, 90%      plasticizers, alkyd                      resins, ore flotation    ______________________________________

Trialkylacetic Acids

Trialkylacetic acids are characterized by the following structure:##STR1## in which R, R', and R" are C_(x) H_(2x+1), with x≧1, andwherein at least one of the R, R' and R" have at least 10 carbon atoms.The series, the products are typically mixtures of isomers, resultingfrom the use of mixed isomer feedstocks and the chemical rearrangementsthat occur in the manufacturing process.

The trialkylacetic acids have a number of uses in areas such aspolymers, pharmaceuticals, agricultural chemicals, cosmetics, andmetal-working fluids. Commercially important derivatives of these acidsinclude acid chlorides, peroxyesters, metal salts, vinyl esters, andglycidyl esters.

The C₁₀ trialkylacetic acids, referred to as neodecanoic acid or asVersatic 10, are liquids at room temperature. These materials aretypically mixtures of isomers.

Metal salts of neodecanoic acid have also been used as catalysts in thepreparation of polymers. For example, bismuth, calcium, barium, andzirconium neodecanoates have been used as catalysts in the formation ofpolyurethane elastomers. Magnesium neodecanoate is one component of acatalyst system for the preparation of polyolefins; vanadium, cobalt,copper, or iron neodecanoates have been used as curing catalysts forconjugated-diene butyl elastomers.

The metal salts of neodecanoic acid have found wide usage as driers forpaints and inks. Metal neodecanoates that are used include silver,cobalt and zirconium, along with lead, copper, manganese, and zinc.

Neodecanoic acid is also used as the carrier for metals in poly(vinylchloride) heat stabilizers. Metals used in this application includebarium, cadmium, and zinc. Tin as the neodecanoate salt has also beenclaimed as a heat stabilizer for maleic anhydride.

One of the growing uses for neodecanoic acid has been in the preparationof adhesion promoters for radial tires. In this application, cobalt ornickel neodecanoate, along with other components, is used during tiremanufacture to promote the adhesion or bonding of the rubber to thesteel cord. The result is high adhesive strength, good thermal agingresistance and improved resistance to moisture aging.

Neodecanoic acid and its esters are used in cosmetics as emollients,emulsifiers, and solubilizers. Zinc or copper salts of neoacids are usedas preservatives for wood.

Aldehydes

Representative aldehydes suitable as the intercalant monomer and/or asthe polar organic carrier in accordance with the present inventioninclude the following:

decyl aldehyde; dodecyl aldehyde; octodecyl aldehyde; eicosan aldehyde;phenyl acetaldehyde; and the like.

Uses

Fatty aldehydes are used in nearly all perfume types and aromas.Polymers and copolymers of aldehydes exist and are of commercialsignificance.

Ketones

Suitable ketones are the organic compounds that contain one or morecarbonyl groups bound to two aliphatic, aromatic, or alicyclicsubstituents, and are represented by the general formula ##STR2##wherein R and/or R' is an alkyl group having at least 10 carbon atoms.

Amines and Amides

Polar organic compounds containing one or more amine or amidefunctionalities that are suitable for use as intercalate monomers and/oras the organic liquid carrier (matrix monomer) in accordance with thepresent invention include all organic amines and/or amides, such as thealkylamines; aminocycloalkanes and substituted aminocycloalkanes;cycloaliphatic diamines; fatty amines; and fatty amides, having a longchain (C₁₀ +) alkyl group and having a dipole moment greater than thedipole moment of water.

Amines and amides are suitable alone, or in admixture, as theintercalant monomer(s) and/or as the organic solvent carrier (matrixmonomer), for intercalation of the phyllosilicate and/or for admixturewith the exfoliated individual platelets of the layered material inproducing the nanocomposite of the present invention. The amines andamides can be any primary, secondary and/or tertiary amines or amides;including the long chain alkyl (C₁₀ +) aliphatic amines; C₁₀ +alkylamines; fatty amines; C₁₀ + alkyl aromatic amines; C₁₀ + alkyldiarylamines; C₁₀ + alkyl substituted alkanolamines; and the like.

Examples of suitable amines that are useful as the intercalant monomerused for intercalation and exfoliation of the layered silicatematerials, and/or as the polar organic carrier for admixture with theindividual platelets in forming nanocomposite compositions are asfollows:

    ______________________________________    REPRESENTATIVE FATTY AMINES                             MOLECULAR    FATTY AMINE              FORMULA    ______________________________________    REPRESENTATIVE PRIMARY AMINES    cocoalkylamines    1-dodecylamine           C.sub.12 H.sub.27 N    1-hexadecylamine         C.sub.16 H.sub.35 N    1-octadecylamine         C.sub.18 H.sub.39 N    oleylamine               C.sub.18 H.sub.37 N    soyaalkylamines    tallowalkylamines    hydrogenated tallowalkylamines    REPRESENTATIVE SECONDARY AMINES    dicocoalkylamines    di-n-dodecylamine        C.sub.24 H.sub.51 N    di-n-hexadecylamine      C.sub.32 H.sub.67 N    di-n-octadecylamine      C.sub.36 H.sub.75 N    ditallowalkylamines    dihydrogenated tallowalkylamines    REPRESENTATIVE TERTIARY AMINES    Alkyldimethyl    cocoalkyldimethylamines    dimethyl-n-octylamine    C.sub.10 H.sub.23 N    dimethyl-n-decylamine    C.sub.12 H.sub.27 N    dimethyl-n-dodecylamine  C.sub.14 H.sub.31 N    dimethyl-n-tetradecylamine                             C.sub.16 H.sub.35leq N    dimethyl-n-hexadecylamine                             C.sub.18 H.sub.39 N    dimethyl-n-octadecylamine                             C.sub.20 H.sub.43 N    dimethyloleylamine       C.sub.20 H.sub.41 N    Dialkylmethyl    di-n-decylmethylamine    C.sub.21 H.sub.45 N    dicocoalkylmethylamines    dihydrogenated    tallowalkylmethylamines    Trialkyl    tri-n-octylamine         C.sub.24 H.sub.51 N    tri-n-dodecylamine       C.sub.36 H.sub.75 N    tri-n-hexadecylamines    ______________________________________

Nonocomposite Uses

Fatty amines and chemical products derived from the amines are used inmany industries. Uses for the nitrogen derivatives are as follows:fabric softeners, oil field chemicals, asphalt emulsifiers, petroleumadditives, and mining.

Amine salts, especially acetate salts prepared by neutralization of afatty amine with acetic acid, are useful as flotation agents(collectors), corrosion inhibitors, and lubricants.

Fatty amines and derivatives are widely used in the oil field, ascorrosion inhibitors, surfactants, emulsifying/deemulsifying and gellingagents. In the mining industry, amines and diamines are used in therecovery and purification of minerals, e.g., by flotation. A significantuse of fatty diamines is as asphalt emulsifiers for preparing asphaltemulsions. Diamines have also been used as epoxy curing agents,corrosion inhibitors, gasoline and fuel oil additives, and pigmentwetting agents. In addition, derivatives of the amines, amphoterics, andlong-chain alkylamines are used as anionic and cationic surfactants inthe personal care industry.

The amides including, primary, secondary and tertiary amides are usefulin accordance with the present invention as intercalant monomers and/oras polar organic carriers that the individual phyllosilicate plateletsare dispersed in. Representative primary fatty amides are as follows:

    ______________________________________    PRIMARY FATTY AMIDE (RCONH.sub.2)                 Molecular    Common Name  Formula    IUPAC Name    ______________________________________    ALKYL    lauramide    C.sub.12 H.sub.25 NO                            dodecylamide    myristamide  C.sub.14 H.sub.29 NO                            tetradecylamide    palmitamide  C.sub.16 H.sub.33 NO                            hexadecylamide    stearamide   C.sub.18 H.sub.37 NO    ALKENYL    palmitoleamide                 C.sub.16 H.sub.31 NO                            hexadecenamide    oleamide     C.sub.18 H.sub.35 NO                            9-octadecenamide    linoleamide  C.sub.18 H.sub.33 NO                            9,12-octadecadienamide    ______________________________________

Polar organic compounds having a long chain (C₁₀ +) alkyl group, andcontaining one or more ether or ester functionalities that are suitablefor use as intercalate monomers and/or as the organic liquid carrier(matrix monomer) in accordance with the present invention include theorganic ethers and/or esters, such as the saturated, unsaturated,cyclic, aromatic, and carboxylic ethers and esters that contain a C₁₀ +alkyl group and having a polar end group that provides the molecule witha dipole moment greater than the dipole moment of water.

Representative Alkyl Nitriles

Suitable nitriles having an alkyl radical of at least 10 carbon atoms,and a dipole moment greater that the dipole moment of water includeundecanonitrile (CH₃ (CH₂)₉ CN); dodecanonitrile (or lauronitrile) (CH₃(CH₂)₁₁ CN); myristonitrile (CH₃ (CH₂)₁₂ CN); pentadecanonitrile (CH₃(CH₂)₁₃ CN); n-heptadecanonitrile (CH₃ (CH₂)₁₅ CN); n-nonadecanitrile(CH₃ (CH₂)₁₇ CN); and mixtures thereof.

Representative N-Alkyl Lactams, Including N-Alkyl Pyrrolidones andCaprolactams ##STR3## n=at least 10, preferably 10-20. RepresentativePyridines

Suitable pyridines include dodecylpyridinium chloride (C₅ H₅ NC₁₂ H₂₅Cl); dodecylpyridinium bromide (C₅ H₅ NC₁₂ H₂₅ Br); hexadecylpyridiniumchloride (C₅ H₅ NC₁₆ H₃₃ Cl); hexadecylpyridinium bromide (C₅ H₅ NC₁₆H₃₃ Br); and mixtures thereof.

Representative N-Alkyl Halides

    C.sub.n H.sub.2n M

n=at least 10, and preferably 10-20,

M=a halogen atom (Cl, F, Br, I, At).

Representative Alkyl-Substituted Lactones ##STR4## n=at least 10,preferably 10-20. Representative Esters

Other useful, representative esters include methyl stearate; ethylstearate; butyl stearate; dodecyl stearate; hexadecyl stearate; dimethylmaleate; dimethyl oxalate; dimethyl adipate; diethyl adipate; di(2-ethylhexyl) adipate; methyl salicylate; ethyl salicylate; methylanthranilate; benzyl cinnamate; and mixtures thereof.

Representative Carboxylic Esters

Plasticizers

Isodecyl adipate;

Epoxidized esters;

Sebacic acid esters, such as dibutyl sebacate;

Stearic acid esters, such as isobutyl stearate.

Surface-Active Agents

Carboxylic acid esters; and anhydrosorbitol esters, such asanhydrosorbitol monolaurate; anhydrosorbitol monooleate; andanhydrosorbitol monostearate.

Ethylene glycol esters, such as ethylene glycol monolaurate.

Ethoxylated anhydrosorbitol esters, such as ethoxylated anhydrosorbitolmonolaurate; ethoxylated anhydrosorbitol monooleate; ethoxylatedanhydrosorbitol monostearate; ethoxylated anhydrosorbitol tristearate;ethylene glycol distearate; and ethylene glycol monostearate.

Glycerol esters, such as glycerol dilaurate; glycerol monooleate; andglycerol monostearate.

Ethoxylated natural fats and oils, such as ethoxylated castor oil,ethoxylated hydrogenated castor oil; and ethoxylated lanolin.

Poly(ethylene glycol) esters, such as poly(ethylene glycol) diester oftall oil acids; poly(ethylene glycol dilaurate); poly(ethylene glycoldistearate); poly(ethylene glycol monolaurate); poly(ethylene glycolmonopalmitate); poly(ethylene glycol monostearate); poly(ethyleneglycol) sesquiester of tall oil acids; poly(glycerol monooleate);poly(glycerol monostearate); and 1,2-propanediol monostearate.

Miscellaneous Esters

Fatty acid esters, not included with plasticizers or surface-activeagents include methyl esters of tallow; and myristyl myristate.

Polyhydric alcohol esters, such as 2-(2-butoxyethoxy) ethyl acetate;2butoxyethyl acetate; and glycerides, mixed C₁₄₋₁₈ and C₁₆₋₁₈, mono- anddi-.

Ethers suitable as the intercalant monomer and/or as the polar organiccarrier (Matrix Monomer) containing dispersed, individual silicateplatelets, containing dispersed, individual silicate platelets, inaccordance with the present invention, are compounds of the generalformula Ar--O--R, and R--O--R' where Ar is an aryl group and R is analkyl group having at least 10 carbon atoms.

In accordance with another embodiment of the present invention, theintercalates can be exfoliated and dispersed into one or moremelt-processible thermoplastic and/or thermosetting matrix oligomers orpolymers, or mixtures thereof. Matrix polymers for use in thisembodiment of the process of this invention may vary widely, the onlyrequirement is that they are melt processible. In this embodiment of theinvention, the polymer includes at least ten (10), preferably at leastthirty (30) recurring monomeric units. The upper limit to the number ofrecurring monomeric units is not critical, provided that the melt indexof the matrix polymer under use conditions is such that the matrixpolymer forms a flowable mixture. Most preferably, the matrix polymerincludes from at least about 10 to about 100 recurring monomeric units.In the most preferred embodiments of this invention, the number ofrecurring units is such that the matrix polymer has a melt index of fromabout 0.01 to about 12grams per 10 minutes at the processingtemperature.

Thermoplastic resins and rubbers for use as matrix polymers in thepractice of this invention may vary widely. Illustrative of usefulthermosplastic resins, which may be used alone or in admixture, arepolyactones such as poly(pivalolactone), poly(caprolactone) and thelike; polyurethanes derived from reaction of diisocyanates such as1,5-naphthalene diisocyanate; p-phenylene diisocyanate, m-phenylenediisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate,4,4'-diphenylisopropylidene diisocyanate, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate,3,3'-dimethoxy-4,4'-biphenyl diisocyanate, dianisidine diisocyanate,toluidine diisocyanate, hexamethylene diisocyanate,4,4'-diisocyanatodiphenylmethane and the like and linear long-chaindiols such as poly(tetramethylene adipate), poly(ethylene adipate),poly(1,4-butylene adipate), poly(ethylene succinate), poly(2,3-butylenesuccinate), polyether diols and the like; polycarbonates such as polymethane bis(4-phenyl) carbonate!, poly 1,1-ether bis(4-phenyl)carbonate!, poly diphenylmethane bis(4-phenyl)carbonate!, poly1,1-cyclohexane bis(4-phenyl)carbonate! and the like; polysulfones;polyethers; polyketones; polyamides such as poly(4-amino butyric acid),poly(hexamethylene adipamide), poly(6-aminohexanoic acid),poly(m-xylylene adipamide), poly(p-xylylene sebacamide),poly(2,2,2-trimethyl hexamethylene terephthalamide), poly(metaphenyleneisophthalamide) (NOMEX), poly(p-phenylene terephthalamide) (KEVLAR), andthe like; polyesters such as poly(ethylene azelate),poly(ethylene-1,5-naphthalate, poly(1,4-cyclohexane dimethyleneterephthalate), poly(ethylene oxybenzoate) (A-TELL), poly(parahydroxybenzoate) (EKONOL), poly(1,4-cyclohexylidene dimethylene terephthalate)(KODEL) (cis), poly(1,4-cyclohexylidene dimethylene terephthalate)(Kodel) (trans), polyethylene terephthalate, polybutylene terephthalateand the like; poly(arylene oxides) such aspoly(2,6-dimethyl-1,4-phenylene oxide), poly(2,6-diphenyl-1,4-phenyleneoxide) and the like; poly(arylene sulfides) such as poly(phenylenesulfide) and the like; polyetherimides; vinyl polymers and theircopolymers such as polyvinyl acetate, polyvinyl alcohol, polyvinylchloride; polyvinyl butyral, polyvinylidene chloride, ethylene-vinylacetate copolymers, and the like; polyacrylics, polyacrylate and theircopolymers such as polyethyl acrylate, poly(n-butyl acrylate),polymethylmethacrylate, polyethyl methacrylate, poly(n-butylmethacrylate), poly(n-propyl methacrylate), polyacrylamide,polyacrylonitrile, polyacrylic acid, ethylene-acrylic acid copolymers,ethylene-vinyl alcohol copolymers acrylonitrile copolymers, methylmethacrylate-styrene copolymers, ethylene-ethyl acrylate copolymers,methacrylated butadiene-styrene copolymers and the like; polyolefinssuch as low density poly(ethylene), poly(propylene), chlorinated lowdensity poly(ethylene), poly(4-methyl-1-pentene), poly(ethylene),poly(styrene), and the like; ionomers; poly(epichlorohydrins);poly(urethane) such as the polymerization product of diols such asglycerin, trimethylol-propane, 1,2,6-hexanetriol, sorbitol,pentaerythritol, polyether polyols, polyester polyols and the like witha polyisocyanate such as 2,4-tolylene diisocyanate, 2,6-tolylenediisocyante, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like; andpolysulfones such as the reaction product of the sodium salt of2,2-bis(4-hydroxyphenyl) propane and 4,4'-dichlorodiphenyl sulfone;furan resins such as poly(furan); cellulose ester plastics such ascellulose acetate, cellulose acetate butyrate, cellulose propionate andthe like; silicones such as poly(dimethyl siloxane), poly(dimethylsiloxane co-phenylmethyl siloxane), and the like; protein plastics; andblends of two or more of the foregoing.

Vulcanizable and thermoplastic rubbers useful as matrix polymers in thepractice of this embodiment of the invention may also vary widely.Illustrative of such rubbers are brominated butyl rubber, chlorinatebutyl rubber, polyurethane elastomers, fluoroelastomers, polyesterelastomers, polyvinylchloride, butadiene/acrylonitrile elastomers,silicone elastomers, poly(butadiene), poly(isobutylene),ethylene-propylene copolymers, ethylene-propylene-diene terpolymers,sulfonated ethylene-propylene-diene terpolymers, poly(chloroprene),poly(2,3-dimethylbutadiene), poly(butadiene-pentadiene),chlorosulphonated poly(ethylenes), poly(sulfide) elastomers, blockcopolymers, made up of segments of glassy or crystalline blocks such aspoly(styrene), poly(vinyl-toluene), poly(t-butyl styrene), polyestersand the like and the elastomeric blocks such as poly(butadiene),poly(isoprene), ethylene-propylene copolymers, ethylene-butylenecopolymers, polyether and the like as for example the copolymers inpoly(styrene)-poly(butadiene)-poly(styrene) block copolymer manufacturedby Shell Chemical Company under the trade name KRATON®.

Useful thermosetting resins useful as matrix polymers include, forexample, the polyamides; polyalkylamides; polyesters; polyurethanes;polycarbonates; polyepoxides; and mixtures thereof.

Most preferred thermoplastic polymers for use as a matrix polymer arethermoplastic polymers such as polyamides, polyesters, and polymers ofalpha-beta unsaturated monomers and copolymers. Polyamides which may beused in the process of the present invention are synthetic linearpolycarbonamides characterized by the presence of recurring carbonamidegroups as an integral part of the polymer chain which are separated fromone another by at least two carbon atoms. Polyamides of this typeinclude polymers, generally known in the art as nylons, obtained fromdiamines and dibasic acids having the recurring unit represented by thegeneral formula:

    --NHCOR.sup.13 COHNR.sup.14 --

in which R¹³ is an alkylene group of at least 2 carbon atoms, preferablyfrom about 2 to about 11, or arylene having at least about 6 carbonatoms, preferably about 6 to about 17 carbon atoms; and R¹⁴ is selectedfrom R¹³ and aryl groups. Also, included are copolyamides andterpolyamides obtained by known methods, for example, by condensation ofhexamethylene diamine and a mixture of dibasic acids consisting ofterephthalic acid and adipic acid. Polyamides of the above descriptionare well-known in the art and include, for example, the copolyamide of30% hexamethylene diammonium isophthalate and 70% hexamethylenediammonium adipate, poly(hexamethylene adipamide) (nylon 6,6),poly(hexamethylene sebacamide) (nylon 6,10), poly(hexamethyleneisophthalamide), poly(hexamethylene terephthalamide),poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylenesuberamide) (nylon 8,8), poly(nonamethylene azelamide) (nylon 9,9)poly(decamethylene azelamide) (nylon 10,9), poly(decamethylenesebacamide) (nylon 10,10), poly bis(4-aminocyclohexyl)methane-1,10-decanecarboxamide)!, poly(m-xylylene adipamide),poly(p-xylylene sebacamide), poly(2,2,2-trimethyl hexamethyleneterephthalamide), poly(piperazine sebacamide), poly(p-phenyleneterephthalamide), poly(metaphenylene isophthalamide) and the like.

Other useful polyamides for use as a matrix polymer are those formed bypolymerization of amino acids and derivatives thereof, as, for example,lactams. Illustrative of these useful polyamides are poly(4-aminobutyricacid) (nylon 4), poly(6-aminohexanoic acid) (nylon 6),poly(7-aminoheptanoic acid) (nylon 7), poly(8-aminooctanoic acid) (nylon8), poly(9-aminononanoic acid) (nylon 9), poly(10-aminodecanoic acid)(nylon 10), poly(11-aminoundecanoic acid) (nylon 11),poly(12-aminododecanoic acid) (nylon 12) and the like.

Preferred polyamides for use as a matrix polymer are poly(caprolactam),poly(12-aminododecanoic acid) and poly(hexamethylene adipamide).

Other matrix or host polymers which may be employed in admixture withexfoliates to form nanocomposites are linear polyesters. The type ofpolyester is not critical and the particular polyesters chosen for usein any particular situation will depend essentially on the physicalproperties and features, i.e., tensile strength, modulus and the like,desired in the final form. Thus, a multiplicity of linear thermoplasticpolyesters having wide variations in physical properties are suitablefor use in admixture with exfoliated layered material platelets inmanufacturing nanocomposites in accordance with this invention.

The particular polyester chosen for use as a matrix polymer can be ahomo-polyester or a copolyester, or mixtures thereof, as desired.Polyesters are normally prepared by the condensation of an organicdicarboxylic acid and an organic diol, and, the reactants can be addedto the intercalates, or exfoliated intercalates for in situpolymerization of the polyester while in contact with the layeredmaterial, before or after exfoliation of the intercalates.

Polyesters which are suitable for use as matrix polymers in thisembodiment of the invention are those which are derived from thecondensation of aromatic, cycloaliphatic, and aliphatic diols withaliphatic, aromatic and cycloaliphatic dicarboxylic acids and may becycloaliphatic, aliphatic or aromatic polyesters.

Exemplary of useful cycloaliphatic, aliphatic and aromatic polyesterswhich can be utilized as matrix polymers in the practice of thisembodiment of the invention are poly(ethylene terephthalate),poly(cyclohexlenedimethylene terephthalate), poly(ethylene dodecate),poly(butylene terephthalate), poly ethylene(2,7-naphthalate)!,poly(methaphenylene isophthalate), poly(glycolic acid), poly(ethylenesuccinate), poly(ethylene adipate), poly(ethylene sebacate),poly(decamethylene azelate), poly(decamethylene adipate),poly(decamethylene sebacate), poly(dimethylpropiolactone),poly(parahydroxybenzoate) (EKONOL), poly(ethylene oxybenzoate) (A-tell),poly(ethylene isophthalate), poly(tetramethylene terephthalate,poly(hexamethylene terephthalate), poly(decamethylene terephthalate),poly(1,4-cyclohexane dimethylene terephthalate) (trans), poly(ethylene1,5-naphthalate), poly(ethylene 2,6-naphthalate),poly(1,4-cyclohexylidene dimethylene terephthalate), (KODEL) (cis), andpoly(1,4-cyclohexylidene dimethylene terephthalate (KODEL) (trans).

Polyester compounds prepared from the condensation of a diol and anaromatic dicarboxylic acid are especially suitable as matrix polymers inaccordance with this embodiment of the present invention. Illustrativeof such useful aromatic carboxylic acids are terephthalic acid,isophthalic acid and a o-phthalic acid, 1,3-naphthalenedicarboxylicacid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylicacid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid,4,4'-diphenylsulfone-dicarboxylic acid,1,1,3-trimethyl-5-carboxy-3-(p-carboxyphenyl)-idane, diphenyl ether4,4'-dicarboxylic acid, bis-p(carboxy-phenyl) methane and the like. Ofthe aforementioned aromatic dicarboxylic acids, those based on a benzenering (such as terephthalic acid, isophthalic acid, orthophthalic acid)are preferred for use in the practice of this invention. Among thesepreferred acid precursors, terephthalic acid is particularly preferredacid precursor.

The most preferred matrix polymer for incorporation with exfoliatesmanufactured in accordance with the present invention is a polymerselected from the group consisting of poly(ethylene terephthalate),poly(butylene terephthalate), poly(1,4-cyclohexane dimethyleneterephthalate), a polyvinylimine, and mixtures thereof. Among thesepolyesters of choice, poly(ethylene terephthalate) and poly(butyleneterephthalate) are most preferred.

Still other useful thermoplastic homopolymers and copolymer matrixpolymers for forming nanocomposites with the exfoliates of the presentinvention are polymers formed by polymerization ofalpha-beta-unsaturated monomers or the formula:

    R.sup.15 R.sup.16 C═CH.sub.2

wherein:

R¹⁵ and R¹⁶ are the same or different and are cyano, phenyl, carboxy,alkylester, halo, alkyl, alkyl substituted with one or more chloro orfluoro, or hydrogen. Illustrative of such preferred homopolymers andcopolymers are homopolymers and copolymers of ethylene, propylene, vinylalcohol, acrylonitrile, vinylidene chloride, esters of acrylic acid,esters of methacrylic acid, chlorotrifluoroethylene, vinyl chloride andthe like. Preferred are poly(propylene), propylene copolymers,poly(ethylene) and ethylene copolymers. More preferred arepoly(ethylene) and poly(propylene).

The mixture may include various optional components which are additivescommonly employed with polar organic liquids. Such optional componentsinclude nucleating agents, fillers, plasticizers, impact modifiers,chain extenders, plasticizers, colorants, mold release lubricants,antistatic agents, pigments, fire retardants, and the like. Theseoptional components and appropriate amounts are well known to thoseskilled in the art.

The amount of intercalated and/or exfoliated layered material includedin the liquid carrier or solvent compositions to form the viscouscompositions suitable to deliver the carrier or some carrier-dissolvedor carrier-dispersed active material, such as a pharmaceutical, may varywidely depending on the intended use and desired viscosity of thecomposition. For example, relatively higher amounts of intercalates,i.e., from about 10% to about 30% by weight of the total composition,are used in forming solvent gels having extremely high viscosities,e.g., 5,000 to 5,000,000 centipoises. Extremely high viscosities,however, also can be achieved with a relatively small concentration ofintercalates and/or exfoliates thereof, e.g., 0.1% to 5% by weight, byadjusting the pH of the composition in the range of about 0-6 or about10-14 and/or by heating the composition above room temperature, e.g., inthe range of about 25° C. to about 200° C., preferably about 75° C. toabout 100° C. It is preferred that the intercalate or platelet loadingbe less than about 10% by weight of the composition. Intercalate orplatelet particle loadings within the range of about 0.01% to about 40%by weight, preferably about 0.05% to about 20%, more preferably about0.5% to about 10% of the total weight of the composition significantlyincreases the viscosity of the composition. In general, the amount ofintercalate and/or platelet particles incorporated into thecarrier/solvent is less than about 20% by weight of the totalcomposition, and preferably from about 0.05% to about 20% by weight ofthe composition, more preferably from about 0.01% to about 10% by weightof the composition, and most preferably from about 0.01% to about 5%,based on the total weight of the composition.

In accordance with an important feature of the present invention, theintercalate and/or platelet/carrier compositions of the presentinvention can be manufactured in a concentrated form, e.g., as a mastergel, e.g, having about 10-90%, preferably about 20-80% intercalateand/or exfoliated platelets of layered material and about 10-90%,preferably about 20-80% carrier/solvent. The master gel can be laterdiluted and mixed with additional carrier or solvent to reduce theviscosity of the composition to a desired level.

The intercalates, and/or exfoliates thereof, are mixed with a carrier orsolvent to produce viscous compositions of the carrier or solventoptionally including one or more active compounds, such as anantiperspirant compound, dissolved or dispersed in the carrier orsolvent.

In accordance with an important feature of the present invention, a widevariety of topically-active compounds can be incorporated into a stablecomposition of the present invention. Such topically active compositionsinclude cosmetic, industrial, and medicinal compounds that act uponcontact with the skin or hair, or are used to adjust rheology ofindustrial greases and the like. In accordance with another importantfeature of the present invention, a topically-active compound can besolubilized in the composition of the present invention or can behomogeneously dispersed throughout the composition as an insoluble,particulate material. In either case topically-effective compositions ofthe present invention are resistant to composition separation andeffectively apply the topically-active compound to the skin or hair. Ifrequired for stability, a surfactant can be included in the composition,such as any disclosed in Laughlin, et al. U.S. Pat. No. 3,929,678,hereby incorporated by reference. In general, the topically-effectivecompositions of the present invention demonstrate essentially no phaseseparation if the topically-active compound is solubilized in thecompositions. Furthermore, if the topically-active compound is insolublein the composition, the composition demonstrates essentially no phaseseparation.

The topically-active compounds can be a cosmetically-active compound, amedically-active compound or any other compound that is useful uponapplication to the skin or hair. Such topically-active compoundsinclude, for example, antiperspirants, antidandruff agents,antibacterial compounds, antifungal compounds, anti-inflammatorycompounds, topical anesthetics, sunscreens and other cosmetic andmedical topically-effective compounds.

Therefore, in accordance with an important feature of the presentinvention, the stable topically-effective composition can include any ofthe generally-known antiperspirant compounds such as finely-dividedsolid astringent salts, for example, aluminum chlorohydrate, aluminumchlorohydrox, zirconium chlorohydrate, and complexes of aluminumchlorohydrate with zirconyl chloride or zirconyl hydroxychloride. Ingeneral, the amount of the antiperspirant compound, such as aluminumzirconium tetrachlorohydrex glycine in the composition can range fromabout 0.01% to about 50%, and preferably from about 0.1% to about 30%,by weight of the total composition.

Other topically-active compounds can be included in the compositions ofthe present invention in an amount sufficient to perform their intendedfunction. For example, zinc oxide, titanium dioxide or similar compoundscan be included if the composition is intended to be a sunscreen.Similarly, topically-active drugs, like antifungal compounds;antibacterial compounds; anti-inflammatory compounds; topicalanesthetics; skin rash, skin disease and dermatitis medications; andanti-itch and irritation-reducing compounds can be included in thecompositions of the present invention. For example, analgesics such asbenzocaine, dyclonine hydrochloride, aloe vera and the like; anestheticssuch as butamben picrate, lidocaine hydrochloride, zylocaine and thelike; antibacterials and antiseptics, such as povidone-iodine, polymyxinb sulfate-bacitracin, zinc-neomycin sulfate-hydrocortisone,chloramphenicol, methylbenzethonium chloride, and erythromycin and thelike; antiparasitics, such as lindane; deodorants, such as chlorophyllincopper complex, aluminum chloride, aluminum chloride hexahydrate, andmethylbenzethonium chloride; essentially all dermatologicals, like acnepreparations, such as benzoyl peroxide, erythromycin-benzoyl peroxide,clindamycin phosphate, 5,7-dichloro-8-hydroxyquinoline, and the like;anti-inflammatory agents, such as alclometasone dipropionate,betamethasone valerate, and the like; burn relief ointments, such aso-amino-p-toluenesulfonamide monoacetate and the like; depigmentingagents, such as monobenzone; dermatitis relief agents, such as theactive steroids amcinonide, diflorasone diacetate, hydrocortisone, andthe like; diaper rash relief agents, such as methylbenzethonium chlorideand the like; emollients and moisturizers, such as mineral oil, PEG-4dilaurate, lanolin oil, petrolatum, mineral wax and the like;fungicides, such as butocouazole nitrate, haloprogin, clotrimazole, andthe like; herpes treatment drugs, such as 9-(2-hydroxyethoxy)methyl!guanine; pruritic medications, such asalclometasone dipropionate, betamethasone valerate, isopropyl myristateMSD, and the like; psoriasis, seborrhea and scabicide agents, such asanthralin, methoxsalen, coal tar and the like; sunscreens, such as octylp-(dimethylamino)benzoate, octyl methoxycinnamate, oxybenzone and thelike; steroids, such as2-(acetyloxy)-9-fluoro-1',2',3',4'-tetrahydro-11-hydroxypregna-1,4-dieno16,17-b! naphthalene-3,20-dione, and21-chloro-9-fluoro-1',2',3',4'-tetrahydro-11b-hydroxypregna-1,4-dieno16z,17-b!naphthalene-3,20-dione. Any other medication capable of topicaladministration also can be incorporated in composition of the presentinvention in an amount sufficient to perform its intended function.

Eventual exfoliation of the intercalated layered material should providedelamination of at least about 90% by weight of the intercalatedmaterial to provide a more viscous composition comprising a carrier orsolvent having monomer-complexed platelet particles substantiallyhomogeneously dispersed therein. Some intercalates require a shear ratethat is greater than about 10 sec⁻¹ for such relatively thoroughexfoliation. Other intercalates exfoliate naturally or by heating, or byapplying low pressure, e.g., 0.5 to 60 atmospheres above ambient, withor without heating. The upper limit for the shear rate is not critical.In the particularly preferred embodiments of the invention, when shearis employed for exfoliation, the shear rate is from greater than about10 sec⁻¹ to about 20,000 sec⁻¹, and in the more preferred embodiments ofthe invention the shear rate is from about 100 sec⁻¹ to about 10,000sec⁻¹.

When shear is employed for exfoliation, any method which can be used toapply a shear to the intercalant/carrier composition can be used. Theshearing action can be provided by any appropriate method, as forexample by mechanical means, by thermal shock, by pressure alteration,or by ultrasonics, all known in the art. In particularly usefulprocedures, the composition is sheared by mechanical methods in whichthe intercalate, with or without the carrier or solvent, is sheared byuse of mechanical means, such as stirrers, Banbury® type mixers,Brabender® type mixers, long continuous mixers, and extruders. Anotherprocedure employs thermal shock in which shearing is achieved byalternatively raising or lowering the temperature of the compositioncausing thermal expansions and resulting in internal stresses whichcause the shear. In still other procedures, shear is achieved by suddenpressure changes in pressure alteration methods; by ultrasonictechniques in which cavitation or resonant vibrations which causeportions of the composition to vibrate or to be excited at differentphases and thus subjected to shear. These methods of shearing are merelyrepresentative of useful methods, and any method known in the art forshearing intercalates may be used.

Mechanical shearing methods may be employed such as by extrusion,injection molding machines, Banbury® type mixers, Brabender® type mixersand the like. Shearing also can be achieved by introducing the layeredmaterial and intercalant monomer at one end of an extruder (single ordouble screw) and receiving the sheared material at the other end of theextruder. The temperature of the layered material/intercalant monomercomposition, the length of the extruder, residence time of thecomposition in the extruder and the design of the extruder (singlescrew, twin screw, number of flights per unit length, channel depth,flight clearance, mixing zone, etc.) are several variables which controlthe amount of shear to be applied for exfoliation.

Exfoliation should be sufficiently thorough to provide at least about80% by weight, preferably at least about 85% by weight, more preferablyat least about 90% by weight, and most preferably at least about 95% byweight delamination of the layers to form two monomer layer tactoidsthat include three platelets or, more preferably, individual plateletparticles that can be substantially homogeneously dispersed in thecarrier or solvent. As formed by this process, the platelet particles orplatelet multi-layer tactoids dispersed in the carrier or solvent havethe thickness of the individual layers plus one to five monolayerthicknesses of complexed monomer, or small multiples less than about 10,preferably less than about 5 and more preferably less than about 3 ofthe layers, and still more preferably 1 or 2 layers. In the preferredembodiments of this invention, intercalation and delamination of everyinterlayer space is complete so that all or substantially all individuallayers delaminate one from the other to form separate platelet particlesfor admixture with the carrier or solvent. The compositions can includethe layered material as all intercalate, completely without exfoliation,initially to provide relatively low viscosities for transportation andpumping until it is desired to increase viscosity via easy exfoliation.In cases where intercalation is incomplete between some layers, thoselayers will not delaminate in the carrier or solvent, and will formplatelet particles comprising those layers in a coplanar aggregate.

The effect of adding into a polar organic liquid carrier the nanoscaleparticulate dispersed platelet particles, derived from the intercalatesformed in accordance with the present invention, typically is anincrease in viscosity.

Molding compositions comprising a thermoplastic or thermosetting polymercontaining a desired loading of platelets obtained from exfoliation ofthe intercalates manufactured according to the invention areoutstandingly suitable for the production of sheets and panels havingvaluable properties. Such sheets and panels may be shaped byconventional processes such as vacuum processing or by hot pressing toform useful objects. The sheets and panels according to the inventionare also suitable as coating materials for other materials comprising,for example, wood, glass, ceramic, metal or other plastics, andoutstanding strengths can be achieved using conventional adhesionpromoters, for example, those based on vinyl resins. The sheets andpanels can also be laminated with other plastic films and this ispreferably effected by co-extrusion, the sheets being bonded in themolten state. The surfaces of the sheets and panels, including those inthe embossed form, can be improved or finished by conventional methods,for example by lacquering or by the application of protective films.

Matrix polymer/platelet composite materials are especially useful forfabrication of extruded films and film laminates, as for example, filmsfor use in food packaging. Such films can be fabricated usingconventional film extrusion techniques. The films are preferably fromabout 10 to about 100 microns, more preferably from about 20 to about100 microns and most preferably from about 25 to about 75 microns inthickness.

The homogeneously distributed platelet particles, exfoliated inaccordance with the present invention, and matrix polymer that form thenanocomposites of one embodiment of the present invention are formedinto a film by suitable film-forming methods. Typically, the compositionis melted and forced through a film forming die. The film of thenanocomposite may go through steps to cause the platelets to be furtheroriented so the major planes through the platelets are substantiallyparallel to the major plane through the film. A method to do this is tobiaxially stretch the film. For example, the film is stretched in theaxial or machine direction by tension rollers pulling the film as it isextruded from the die. The film is simultaneously stretched in thetransverse direction by clamping the edges of the film and drawing themapart. Alternatively, the film is stretched in the transverse directionby using a tubular film die and blowing the film up as it passes fromthe tubular film die. The films may exhibit one or more of the followingbenefits: increased modulus; increased wet strength; increaseddimensional stability; decreased moisture adsorption; decreasedpermeability to gases such as oxygen and liquids, such as water,alcohols and other solvents.

The following specific examples are presented to more particularlyillustrate the invention and are not to be construed as limitationsthereon.

The graphs of FIGS. 5-11 are x-ray diffraction patterns of blends ofvarious amounts of dodecyl pyrrolidone monomer intercalant with sodiumbentonite clay (containing a crystobalite impurity). The d(001) peak ofnon-exfoliated (layered) sodium bentonite clay appears at about 12.5 Å,as shown in the mechanical blends of powdered sodium bentonite clay(containing about 10-12% by weight water) with powdered monomerintercalants, at various monomer intercalant loadings. When themechanical blends were then heated to the intercalant monomer melttemperature, and preferably at least about 40-50° C. above theintercalant monomer melt temperature for faster reaction, the monomermelt was intercalated between the bentonite clay platelets, and anexothermic reaction occurred that, it is theorized, resulted from theintercalant monomer being bonded to the internal faces of the clayplatelets sufficiently for exfoliation of the intercalated clay. Itshould be noted, also, that intercalation did not occur unless thebentonite clay included water in an amount of at least about 5% byweight, based on the dry weight of the clay, preferably at least about10% to about 15% water. The water can be included in the clay asreceived, or can be added to the clay prior to or during intercalantmonomer melt or solution contact.

As shown in FIG. 5, the melted blend of 10% dodecyl pyrrolidone, 90%sodium montmorillonite clay does not include a d(001) peak at about 12.5Å (the layered clay was no longer present in the blend), but shows ad(020) peak at about 15 Å that is representative of intercalation. Itshould also be noted that the intercalation occurred withoutshearing--the layered clay intercalates naturally after sufficientexposure to intercalant monomer.

FIG. 6 is an x-ray diffraction pattern for a melted blend (complex) ofdodecyl pyrrolidone (DDP) and sodium montmorillonite clay at 20% byweight DDP and 80% by weight sodium montmorillonite or approximately a1:1 molar ratio of DDP and sodium. It should be noted that at or abovethe 1:1 molar ratio of DDP to sodium (on the inner platelet surfaces ofthe sodium montmorillonite clay) a strong peak occurs at about 35 Å,with the peak at about 15 Å (e.g., 15.99 Å) becoming less significant.As the molar ratio of DDP to sodium is increased (FIGS. 7-11), the peakat about 35 Å moves slightly higher (up to about 44 Å) and becomesstronger (as indicated by a more narrow peak), while the peak at about15 Å becomes less and less significant. At a weight ratio of about 40%DDP and 60% sodium (FIG. 8) or a 2:1 molar ratio of DDP to sodium, asecond order peak appears at about 18 Å, and the peak at 15 Å hasdisappeared. At this molar ratio of 2:1 there are two DDP moleculessurrounding each montmorillonite inner platelet sodium ion to providetwo long chain (C₁₂) rigid tails extending perpendicularly from theinner sodium montmorillonite platelet surfaces. At 50% by weight DDP,50% sodium montmorillonite (FIG. 9) a third order peak appears at about14.6 Å signifying that a third DDP molecule has coordinated surroundingeach sodium ion on the platelet surfaces of the sodium montmorilloniteclay, thereby providing three orders of diffraction for the intercalatedclay. As more DDP molecules coordinate to surround the Na⁺ ions on theinner platelet surfaces of the sodium montmorillonite clay, theperpendicularly extending long chain (C₁₂) tails become more and morerigid, and some of the C₁₂ tails abut C₁₂ tail ends of DDP moleculesextending perpendicularly from Na⁺ ions on an adjacent sodiummontmorillonite platelet surface. The abutting rigid tail ends of theC₁₂ radical of the DDP molecules provide surprising separation ofadjacent sodium montmorillonite platelets at relatively low loadings ofDDP and other long chain alkyl (C₁₀ + alkyl) organic molecules thatinclude a molecule end having a dipole moment greater than the dipolemoment of water. As shown in FIGS. 10 and 11, at 60% and 80% by weightDDP, fifth and higher orders of diffraction occur, indicating more DDPmolecules surrounding the Na⁺ ions on the inner platelet surfaces of thesodium montmorillonite clay. FIG. 12 shows the same type ofintercalation using dodecyl aldehyde as the monomer intercalant. Similarresults also are achieved with stearic acid and other C₁₀ + alkylorganic monomers having a dipole moment at one molecule end that isgreater than the dipole moment of water.

Since wide basal spacings can be achieved using relatively fewintercalant molecules, due to the rigidity of the extending long chainalkyl tails of the intercalant molecules; and due to the abutment ofsome of the long chain alkyl tails extending in opposite directions fromcations of adjacent montmorillonite platelets, the gallery ofintercalant molecules extending from the surfaces of the intercalate andexfoliate platelets can be relatively sparse and untangled, resulting inexceptional sorption (absorption and/or adsorption) of both hydrophilicand hydrophobic liquids and gases. Monomer intercalants having an alkylradical with less than about 10 carbon atoms require far more monomer toachieve similar basal spacings and, therefore, are capable of sorbingfor less liquid and gas molecules.

EXAMPLE 2

An intercalate, formed as in the previous example between dodecylpyrrolidone (DDP) and sodium montmorillonite clay at a 2:1 weight ratio,was compounded into polybutylene terephthalate (PBT) polymer at 30percent by weight of the intercalate, 70 weight percent PBT. Thisconcentrate was then further compounded into PBT to yield a finalnanocomposite with 6.3% by weight DDP-complexed clay platelets (thenanocomposite).

The following table contains a comparison of the physical properties ofpure PBT and its composite.

    __________________________________________________________________________    Data for PBT Composities Containing AMS*-DDP    INSTRON                                    DMA                          Modulus         HDT  Flexural                          (MPa)      Energy to                                          HDT° C.                                               Modulus    Sample          Maximum                Maximum                     Modulus                          (75° C.)                                Impact                                     Break                                          66 psi                                               at 23° C.    Description          Load (MPa)                Strain (%)                     (MPa)                          (above Tg)                                St. (J/m)                                     (kgf-mm)                                          264 psi                                               (MPa)    __________________________________________________________________________    6.3% AMS          55.4  2.65 3083.8                          1000  21.4 397.2                                          91   3056.9    (DDP)/PBT    Pure PBT          50.5  >58.2                     2324  500  56.0 9551.7                                          54.0 2139.3    __________________________________________________________________________     *AMS = sodium montmorillonite clay

The composite has substantially better tensile strength, modulas, andheat distortion temperature (HDT). FIG. 13 compares the dynamicmechanical analyses (DMA) of the flexural modulus for pure PBT (lowercurve) and the nanocomposite (upper curve).

At a temperature below the glass transition temperature (Tg) of the PBTmatrix polymer, e.g., 25° C., the clay platelet--DDP complex increasesthe flexural modulus increases from about 2.1×10⁹ Pa to about 3.1×10⁹ Paor about 48%. Surprisingly, at a temperature above the glass transitiontemperature of the PBT matrix polymer, e.g., 75° C., the flexuralmodulus increases from about 0.45×10⁹ Pa to about 0.95×10⁹ Pa, or abouta 100% increase in flexural modulus.

Numerous modifications and alternative embodiments of the invention willbe apparent to those skilled in the art in view of the foregoingdescription. Accordingly, this description is to be construed asillustrative only and is for the purpose of teaching those skilled inthe art the best mode of carrying out the invention. The details of theprocess may be varied substantially without departing from the spirit ofthe invention, and the exclusive use of all modifications which comewithin the scope of the appended claims is reserved.

What is claimed is:
 1. An intercalate, capable of being exfoliated,formed by contacting a phyllosilicate, having a moisture content of atleast about 4% by weight, with an intercalant monomer having an alkylradical of at least 10 carbon atoms in length and having a polar moietyat one end that has a dipole moment greater than the dipole moment ofwater, to form an intercalating composition, said intercalatingcomposition having a weight ratio of intercalant monomer tophyllosilicate of at least about 1:20, to achieve sorption andcomplexing of the intercalant monomer, thereby forming said intercalate,through a mechanism selected from the group consisting of ioniccomplexing; electrostatic complexing; chelation; hydrogen bonding;ion-dipole; dipole/dipole; Van Der Waals forces; and any combinationthereof, between adjacent spaced layers of the phyllosilicate without anonium ion or silane coupling agent to expand the spacing between apredominance of the adjacent platelets of said phyllosilicate to atleast about 5 Å, when measured after sorption of intercalant monomer anddrying to a maximum of 5% by weight water.
 2. An intercalate inaccordance with claim 1, wherein the concentration of intercalantmonomer in said intercalating composition is at least about 0.1% byweight, based on the weight of water and intercalant monomer in theintercalating composition.
 3. An intercalate in accordance with claim 2,wherein the concentration of intercalant monomer in said intercalatingcomposition is at least about 1% by weight.
 4. An intercalate inaccordance with claim 3, wherein the concentration of intercalantmonomer in said intercalating composition is at least about 2% byweight.
 5. An intercalate in accordance with claim 4, wherein theconcentration of intercalant monomer in said intercalating compositionis at least about 30% by weight.
 6. An intercalate in accordance withclaim 4, wherein the concentration of intercalant monomer in saidintercalating composition is in the range of about 10% to about 60% byweight.
 7. An intercalate in accordance with claim 5, wherein theconcentration of intercalant monomer in said intercalating compositionin the range of about 50% to about 90% by weight.
 8. An intercalate inaccordance with claim 1, wherein the concentration of intercalantmonomer in the intercalating composition is at least about 16% byweight, based on the dry weight of the layered material contacted.
 9. Anintercalate in accordance with claim 8, wherein the concentration ofintercalant monomer in the intercalating composition is in the range ofabout 16% to about 70% by weight, based on the dry weight of the layeredmaterial contacted.
 10. An intercalate in accordance with claim 9,wherein the concentration of intercalant monomer in the intercalatingcomposition is in the range of about 16% to less than about 35% byweight, based on the dry weight of the layered material contacted. 11.An intercalate in accordance with claim 9, wherein the concentration ofintercalant monomer in the intercalating composition is in the range ofabout 35% to less than about 55% by weight, based on the dry weight ofthe layered material contacted.
 12. An intercalate in accordance withclaim 9, wherein the concentration of the intercalant monomer in theintercalating composition is in the range of about 55% to less thanabout 70% by weight, based on the dry weight of the layered materialcontacted.
 13. An intercalate in accordance with claim 1, wherein theintercalant monomer is an alcohol having an alkyl radical of 10 to 24carbon atoms.
 14. An intercalate in accordance with claim 1, wherein theintercalant monomer is selected from alcohols and polyhydric alcohols.15. A method of exfoliating a phyllosilicate comprising:contacting thephyllosilicate, having a moisture content of at least about 4% byweight, with an intercalant monomer having an alkyl radical of at least10 carbon atoms in length and having a polar moiety at one end that hasa dipole moment greater than the dipole moment of water, to form anintercalating composition comprising at least about 2% by weight of saidintercalant monomer, to achieve intercalation of said monomer betweensaid adjacent phyllosilicate platelets, without an onium ion or silanecoupling agent, in an amount sufficient to space said adjacentphyllosilicate platelets a distance of at least about 5 Å; andseparating the platelets of the intercalated phyllosilicate.
 16. Themethod of claim 15, wherein said intercalating composition includes awater carrier comprising about 5% to about 50% by weight water, based onthe total weight of said intercalating composition.
 17. The method ofclaim 16, wherein said intercalating composition comprises about 10% toabout 40% by weight water.
 18. A composition comprising an organicliquid carrier in an amount of about 40% to about 99.95% by weight ofthe composite material, and about 0.05% to about 60% by weight of anintercalated phyllosilicate material, said intercalated phyllosilicatematerial formed by contacting a phyllosilicate, having a water contentof at least about 4% by weight, with an intercalant monomer having analkyl radical of at least 10 carbon atoms in length and having a polarmoiety at one end that has a dipole moment greater than the dipolemoment of water, to form an intercalating composition, having a weightratio of intercalant monomer:phyllosilicate of at least about 1:20 toachieve sorption of the intercalant monomer between adjacent spacedlayers of the phyllosilicate, without an onium ion or silane couplingagent, to expand the spacing between a predominance of the adjacentphyllosilicate platelets at least about 5 Å, when measured aftersorption of the intercalant monomer and at a maximum water content ofabout 5% by weight, based on the dry weight of the phyllosilicate. 19.The composition of claim 18, wherein the intercalate is exfoliated intoa predominance of individual platelets.
 20. A composition in accordancewith claim 18, wherein said intercalating composition comprises thephyllosilicate, an intercalant monomer and water, and wherein theconcentration of intercalant monomer in said intercalating compositionis at least about 4% by weight, based on the dry weight of thephyllosilicate in the intercalating composition.
 21. A composition inaccordance with claim 20, wherein the concentration of intercalantmonomer in said intercalating composition is at least about 15% byweight, based on the dry weight of the phyllosilicate in theintercalating composition.
 22. A composition in accordance with claim21, wherein the concentration of intercalant monomer in saidintercalating composition is at least about 20% by weight.
 23. Acomposition in accordance with claim 22, wherein the concentration ofintercalant monomer in said intercalating composition is at least about30% by weight.
 24. A composition in accordance with claim 23, whereinthe concentration of intercalant monomer in said intercalatingcomposition in the range of about 50% to about 80% by weight.
 25. Acomposition in accordance with claim 23, wherein the concentration ofintercalant monomer in said intercalating composition in the range ofabout 50% to about 100% by weight.
 26. A composition in accordance withclaim 18, wherein the concentration of intercalant monomer in theintercalating composition is at least about 16% by weight.
 27. Acomposition in accordance with claim 26, wherein the concentration ofintercalant monomer in the intercalating composition is in the range ofabout 16% to about 70% by weight.
 28. A composition in accordance withclaim 27, wherein the concentration of intercalant monomer in theintercalating composition is in the range of about 16% to less thanabout 35% by weight.
 29. A composition in accordance with claim 27,wherein the concentration of intercalant monomer in the intercalatingcomposition is in the range of about 35% to less than about 55% byweight.
 30. A composition in accordance with claim 27, wherein theconcentration of the intercalant monomer in the intercalatingcomposition is in the range of about 55% to less than about 70% byweight.
 31. A composition in accordance with claim 18, further includinga matrix polymer selected from the group consisting of a polyamide;polyvinyl alcohol; polycarbonate; polyvinylimine; polyvinylpyrrolidone;polyethylene terephthalate; polybutylene terephthalate; a polymerpolymerized from a monomer selected from the group consisting ofdihydroxyethyl terephthalate; dihydroxybutyl terephthalate;hydroxyethylmethyl terephthalate; hydroxybutylmethyl terephthalate; andmixtures thereof.
 32. A composition in accordance with claim 31, whereinthe matrix polymer is a mixture of a polymer of hydroxyethylterephthalate with a polymer polymerized from a monomer selected fromthe group consisting of dihydroxyethyl terephthalate and dihydroxybutylterephthalate, and mixtures thereof.
 33. A composition in accordancewith claim 31, wherein the matrix polymer is polyethylene terephthalate.34. A method of manufacturing a composite material containing about 10%to about 99.95% by weight of a matrix polymer selected from the groupconsisting of a thermoplastic polymer, a thermosetting polymer, andmixtures thereof, and about 0.05% to about 60% by weight of exfoliatedplatelets of a phyllosilicate material, said platelets derived from anintercalated phyllosilicate having an intercalant monomer intercalatedbetween and bonded to an inner surface of the phyllosilicate plateletsthrough a bonding mechanism selected from the group consisting of ioniccomplexing; electrostatic complexing; chelation; hydrogen bonding;ion-dipole; dipole/dipole; Van Der Waals forces; and any combinationthereof, comprising:contacting the phyllosilicate, having a moisturecontact of about 4% by weight, with water and an intercalant monomer,said intercalant monomer including an alkyl radical having at least 10carbon atoms in length and having a polar moiety at one end that has adipole moment greater than the dipole moment of water, to achieveintercalation of said intercalant monomer between said adjacentphyllosilicate platelets in an amount sufficient to space said adjacentphyllosilicate platelets a distance of at least about 5 Å, without anonium ion or silane coupling agent; combining the intercalate with saidmatrix polymer; exfoliating the spaced platelets of said intercalateinto predominantly individual platelets; and dispersing said exfoliatedplatelets throughout said matrix polymer.
 35. The method of claim 34,wherein said phyllosilicate is contacted with said water in anintercalating composition including said water, said intercalantmonomer, said phyllosilicate, and a liquid polar organic hydrocarboncarrier, and wherein said intercalating composition comprises about 5%to about 50% by weight water, based on the dry weight of saidphyllosilicate.
 36. The method of claim 35, wherein said intercalatingcomposition comprises about 10% to about 90% by weight of said polarorganic liquid hydrocarbon, based on the dry weight of thephyllosilicate.
 37. A method of manufacturing a composition comprisingan organic liquid and a phyllosilicate intercalate comprising:contactingthe phyllosilicate with an intercalant monomer having an alkyl radicalof at least 10 carbon atoms in length and having a polar moiety at oneend that has a dipole moment greater than the dipole moment of water,and water, to form an intercalating composition, wherein the weightratio of the intercalant monomer to phyllosilicate in said intercalatingcomposition is at least about 1 to 20, and the concentration of saidintercalant monomer in said intercalating composition is at least about5% up to about 90% intercalant monomer, based on the dry weight of thephyllosilicate, to form an intercalate having said intercalant monomerintercalated between said adjacent phyllosilicate platelets in an amountsufficient to space said adjacent phyllosilicate platelets a distance ofat least about 5 Å, without an onium ion or silane coupling agent; andcombining the intercalate with said organic liquid.
 38. A compositematerial comprising a matrix polymer in an amount of about 40% to about99.95% by weight of the composite material, and about 0.05% to about 60%by weight exfoliated platelets of a phyllosilicate material, saidplatelets derived from an intercalate formed by contacting aphyllosilicate with an intercalant monomer, said intercalant monomerhaving an alkyl radical of at least 10 carbon atoms in length and havinga polar moiety at one end that has a dipole moment greater than thedipole moment of water, without a coupling agent selected from the groupconsisting of onium ion and silane coupling agents, to form anintercalating composition, said intercalating composition having aconcentration of said intercalant monomer of at least about 2% by weightintercalant monomer, and in a quantity sufficient to incorporate a layerof monomer between adjacent phyllosilicate platelets of sufficientthickness for exfoliation of said platelets, to achieve sorption of theintercalant monomer having alkyl radicals extending perpendicular to thephyllosilicate platelets to expand the spacing between a predominance ofthe adjacent phyllosilicate platelets at least about 5 Å, when measuredafter sorption of the intercalant monomer.
 39. A composite material inaccordance with claim 38, wherein the quantity of intercalant monomer insaid intercalating composition is about 16% to about 80% by weight,based on the weight of phyllosilicate contacted by said intercalatingcomposition.
 40. A method of manufacturing a composite materialcontaining about 40% to about 99.95% by weight of a matrix thermoplasticor thermosetting polymer, and about 0.05% to about 60% by weight ofexfoliated platelets of a phyllosilicate material, said plateletsderived from an intercalated phyllosilicate having an intercalantmonomer intercalated between adjacent phyllosilicate plateletscomprising:contacting the phyllosilicate with an intercalant monomerhaving an alkyl radical of at least 10 carbon atoms in length and havinga polar moiety at one end that has a dipole moment greater than thedipole moment of water, without first contacting the phyllosilicate witha coupling agent selected from the group consisting of onium ion andsilane coupling agents, to form an intercalating composition, saidintercalating composition comprising at least about 5% by weight of saidintercalant monomer in a quantity sufficient to incorporate a layer ofintercalant monomer between adjacent phyllosilicate platelets ofsufficient thickness for exfoliation of said platelets, to achieveintercalation of said intercalant monomer between said adjacentphyllosilicate platelets in an amount sufficient to space said adjacentphyllosilicate platelets a distance of at least about 5 Å; combining theintercalated platelets with said thermoplastic or thermosetting polymer,and heating the polymer sufficiently to provide for flow of said polymerand delamination of the platelets of said phyllosilicate; and dispersingsaid delaminated platelets throughout said matrix polymer.
 41. A methodin accordance with claim 40, wherein the intercalating compositionincludes about 16% to about 80% by weight intercalant monomer, based onthe weight of phyllosilicate contacted by said intercalatingcomposition.
 42. An intercalate in accordance with claim 1, wherein theamount of intercalant monomer intercalated into the phyllosilicatematerial is 10-90% monomer based on the dry weight of the phyllosilicatematerial.
 43. An intercalate in accordance with claim 42, wherein theamount of intercalant monomer intercalated into the phyllosilicatematerial is about 15% to about 80%, based on the dry weight of thephyllosilicate material.
 44. An intercalate in accordance with claim 43,wherein the weight ratio of intercalated monomer to phyllosilicatematerial is from about 16 grams of intercalant monomer per 100 grams ofphyllosilicate material to about 80 grams of intercalant monomer per 100grams of phyllosilicate material.
 45. An intercalate in accordance withclaim 44, wherein the weight ratio of intercalated monomer tophyllosilicate material is from about 20 grams of intercalant monomerper 100 grams of phyllosilicate material to about 60 grams ofintercalant monomer per 100 grams of phyllosilicate material.
 46. Anintercalate in accordance with claim 1, wherein the weight ratio ofintercalant monomer to phyllosilicate material in the intercalatingcomposition is in the range of 1:20 to 1:3.
 47. A method in accordancewith claim 15, wherein the amount of intercalant monomer intercalatedinto the phyllosilicate material is 10-90% intercalant monomer, based onthe dry weight of the phyllosilicate material.
 48. A method inaccordance with claim 47, wherein the amount of intercalant monomerintercalated into the phyllosilicate material is about 15% to about 80%,based on the dry weight of the phyllosilicate material.
 49. A method inaccordance with claim 48, wherein the weight ratio of intercalatedmonomer to phyllosilicate material is from about 16 grams of intercalantmonomer per 100 grams of phyllosilicate material to about 80 grams ofintercalant monomer per 100 grams of phyllosilicate material.
 50. Amethod in accordance with claim 49, wherein the weight ratio ofintercalated monomer to phyllosilicate material is from about 20 gramsof intercalant monomer per 100 grams of phyllosilicate material to about60 grams of intercalant monomer per 100 grams of phyllosilicatematerial.
 51. A method in accordance with claim 15, wherein the weightratio of intercalant monomer to phyllosilicate material in theintercalating composition is in the range of 1:20 to 1:3.
 52. Acomposition in accordance with claim 18, wherein the amount ofintercalant monomer intercalated into the phyllosilicate material is10-90% intercalant monomer, based on the dry weight of thephyllosilicate material.
 53. A composition in accordance with claim 52,wherein the amount of intercalant monomer intercalated into thephyllosilicate material is 15-80% intercalant monomer, based on the dryweight of the phyllosilicate material.
 54. A composition in accordancewith claim 53, wherein the weight ratio of intercalated monomer tophyllosilicate material is from about 16 grams of intercalant monomerper 100 grams of phyllosilicate material to about 80 grams ofintercalant monomer per 100 grams of phyllosilicate material.
 55. Acomposition in accordance with claim 18, wherein the weight ratio ofintercalant monomer to phyllosilicate material in the intercalatingcomposition is in the range of 1:20 to 1:3.
 56. A method in accordancewith claim 34, wherein the amount of intercalant monomer intercalatedinto the phyllosilicate material is 10-90% intercalant monomer, based onthe dry weight of the phyllosilicate material.
 57. A method inaccordance with claim 56, wherein the amount of intercalant monomerintercalated into the phyllosilicate material is about 15% to about 80%intercalant monomer, based on the dry weight of the phyllosilicatematerial.
 58. A method in accordance with claim 57, wherein the weightratio of intercalated monomer to phyllosilicate material is from about16 grams of intercalant monomer per 100 grams of phyllosilicate materialto about 80 grams of intercalant monomer per 100 grams of phyllosilicatematerial.
 59. A method in accordance with claim 58, wherein the weightratio of intercalated monomer to phyllosilicate material is from about20 grams of intercalant monomer per 100 grams of phyllosilicate materialto about 60 grams of intercalant monomer per 100 grams of phyllosilicatematerial.
 60. A method in accordance with claim 34, wherein the weightratio of intercalant monomer to phyllosilicate in the intercalatingcomposition is in the range of 1:20 to 1:3.
 61. A method in accordancewith claim 37, wherein the intercalating composition includes about 16%to about 80% by weight intercalant monomer, based on the weight ofphyllosilicate contacted by said intercalating composition.
 62. A methodin accordance with claim 37, wherein the amount of intercalant monomerintercalated into the phyllosilicate material is 10-90% monomer based onthe dry weight of the phyllosilicate material.
 63. A method inaccordance with claim 62, wherein the amount of intercalant monomerintercalated into the phyllosilicate material is about 15% to about 80%,based on the dry weight of the phyllosilicate material.
 64. A method inaccordance with claim 63, wherein the weight ratio of intercalatedmonomer to phyllosilicate material is from about 16 grams of intercalantmonomer per 100 grams of phyllosilicate material to about 80 grams ofintercalant monomer per 100 grams of phyllosilicate material.
 65. Amethod in accordance with claim 64, wherein the weight ratio ofintercalated monomer to phyllosilicate material is from about 20 gramsof intercalant monomer per 100 grams of phyllosilicate material to about60 grams of intercalant monomer per 100 grams of phyllosilicatematerial.
 66. A method in accordance with claim 37, wherein the weightratio of intercalant monomer to phyllosilicate material in theintercalating composition is in the range of 1:20 to 1:3.